KR20190109205A - A light converting resin composition, a light converting unit and a display device using the same - Google Patents

Abstract

The present invention relates to a light conversion resin composition, which comprises: two or more kinds of quantum dots of which emission center wavelengths differ by 50 nm or more from each other; and a binder resin, wherein the binder resin includes a cardo-based binder resin and an epoxy-containing acrylic binder resin, the quantum dots comprise a polyethylene glycol-based ligand disposed on a surface, and the polyethylene glycol ligand includes a compound represented by chemical formula 1-A, thereby having excellent brightness and long-term reliability, to a light conversion laminated substrate, and to an image display device using the same.

Description

Light conversion resin composition and light conversion laminated substrate, image display device using the same {A LIGHT CONVERTING RESIN COMPOSITION, A LIGHT CONVERTING UNIT AND A DISPLAY DEVICE USING THE SAME}

The present invention relates to a light conversion resin composition and a light conversion laminated substrate, and an image display device using the same.

In liquid crystal display (LCD) TVs that use a light emitting diode (LED) as a back light unit (BLU), LED BLU is one of the most important parts of an LCD TV.

As a method of forming a white LED BLU, a combination of red (R, R), green (G), and blue (B) LED chips is usually used to form a white LED BLU, or a wide half width with a blue LED chip. White is realized by using a combination of yellow (Yellow, Y) phosphors having a light emission wavelength of.

However, when combining red, green, and blue LED chips, there is a problem in that manufacturing cost is high depending on the number of LED chips and a complicated process, and when combining yellow phosphors on a blue LED chip, wavelengths of green and red are combined. Since the color purity is lowered and the color reproducibility is deteriorated, the optical film including the quantum dots is applied to a backlight using a blue LED chip, thereby improving color reproducibility and luminance of an image display device. have.

However, in the preparation of coating compositions, solvents such as toluene, hexane, and chloroform are inevitably used using ligands of very low polarity compounds, so that a worker has to work in an environment exposed to harmful solvents.

In addition, in the case of the optical film, a structure such as a barrier layer, a base layer, etc., in addition to the light emitting layer including the quantum dots is complicated, thereby lowering the luminance of emitted light of the quantum dots. In addition, the problem that the quantum dot is extinguished when the film is produced at a high temperature during the manufacturing process, there is a problem in the long-term reliability as the process proceeds at a low process temperature in order to process the optical film form, there is a need for improvement.

Republic of Korea Patent No. 10-1718592 is a quantum dot; Scattering particles of a core shell structure including a TiO ₂ core part and a shell part including SiO ₂ covering at least a portion of a surface of the core part; And a quantum dot composition comprising a curable resin, wherein the scattering particles are based on the total weight of the solid content of the quantum dot composition to provide a quantum dot composition of 5% by weight or more 50% by weight.

Republic of Korea Patent No. 10-1690624 is a plurality of non-cadmium-based quantum dots dispersed in a polymer resin, one or both sides of the polymer resin layer patterned; A first barrier film formed on one surface of the polymer resin layer; And a second barrier film formed on another surface of the polymer resin layer, wherein the bottom surface of the polymer resin layer is prism patterned or lens patterned, and the bottom surface of the polymer resin layer is prism patterned. The pitch of the prism pattern is 20 to 70㎛, the vertex angle is 95 to 120 °, the cross section of the pattern is a triangle, the pitch of the lens pattern is 20 to 70 when the lower surface of the polymer resin layer is a lens patterning There is provided an optical sheet having a semi-circular cross section, wherein the ratio of pitch to height is 4: 1 to 10: 1, and the pattern is semicircular.

In addition, in the case of the optical sheet, the structure is complicated, thereby lowering the emission luminance of the quantum dot and the firing temperature is low, thereby causing a problem of low long-term reliability.

Republic of Korea Patent No. 10-1718592 (2017.03.15.LG Chem Co., Ltd.) Republic of Korea Patent No. 10-1690624 (2016.12.22. Kolon Industries Co., Ltd.)

The present invention is to solve the problems as described above, by including an acrylic binder resin containing a cardo-based binder resin and an epoxy, a light conversion resin composition and a light conversion laminated substrate having excellent brightness and long-term reliability, an image display device using the same The purpose is to provide.

In addition, the present invention is a light conversion resin composition and light conversion laminated substrate, which can improve the excellent dispersibility and optical properties by including two or more kinds of quantum dots in which the emission center wavelength is 50nm or more different from each other, and introduced a new ligand, using the same Its purpose is to provide an image display apparatus.

The optical conversion resin composition according to the present invention for achieving the above object is two or more kinds of quantum dots that the emission center wavelength is different from each other by more than 50nm; And a binder resin; wherein the binder resin includes a cardo-based binder resin and an epoxy-containing acrylic binder resin, and the quantum dots include polyethylene glycol-based ligands disposed on a surface thereof, and the polyethylene glycol-based ligand is represented by the following chemical formula: It is characterized by including the compound represented by 1-A.

[Formula 1-A]

(In Chemical Formula 1-A,

R 'is represented by the formula 1-1,

[Formula 1-1]

In Chemical Formula 1-1,

R1 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

R2 is represented by the formula 1-2,

[Formula 1-2]

In Chemical Formula 1-2,

A is an oxygen atom or a sulfur atom,

R3 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

), 카르복실산(

), 디티오아세트산(

), 인산(

) 또는 아민(-NH₂)이고,B is mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

) Or amine (-NH ₂ ),

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(-NH₂), 탄소수 1 내지 20의 직쇄 알킬기 또는 탄소수 3 내지 20의 분지쇄 알킬기이고, R “is hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms,

k is an integer from 1 to 100,

l is an integer from 0 to 1,

m is an integer from 0 to 10).

The photoconversion resin composition according to the present invention comprises an acrylic binder resin containing a cardo binder resin and an epoxy, so that the formation temperature of the coating layer can be effectively processed at 100 to 250 degrees, and the effect of excellent brightness characteristics and long-term reliability have.

In addition, the light conversion resin composition according to the present invention has a difference in emission center wavelength by 50 nm or more, and includes two or more kinds of quantum dots incorporating a new ligand, thereby providing excellent dispersibility and optical properties.

The light conversion substrate and the image display device using the light conversion laminated substrate made of the light conversion resin composition has an excellent effect of reliability.

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

< Light conversion  Resin Composition>

The photoconversion resin composition of the present invention comprises at least two quantum dots in which the emission center wavelengths differ from each other by 50 nm or more; And a binder resin, wherein the binder resin includes a cardo-based binder resin and an epoxy-containing acrylic binder resin, and the quantum dots include polyethylene glycol-based ligands disposed on a surface thereof, and the polyethylene glycol-based ligand is represented by the following chemical formula: It is characterized by including the compound represented by 1-A.

[Formula 1-A]

(In Chemical Formula 1-A,

R 'is represented by the formula 1-1,

[Formula 1-1]

In Chemical Formula 1-1,

R1 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

R2 is represented by the formula 1-2,

[Formula 1-2]

In Chemical Formula 1-2,

A is an oxygen atom or a sulfur atom,

R3 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

), 카르복실산(

), 디티오아세트산(

), 인산(

) 또는 아민(-NH₂)이고,B is mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

) Or amine (-NH ₂ ),

), 디티오아세트산(

), 인산(

), 아민(-NH₂), 탄소수 1 내지 20의 직쇄 알킬기 또는 탄소수 3 내지 20의 분지쇄 알킬기이고, R “is hydrogen atom, mercapto ( ), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms,

k is an integer from 1 to 100,

l is an integer from 0 to 1,

m is an integer from 0 to 10).

Quantum dots

The photoconversion resin composition according to the present invention includes two or more kinds of quantum dots having different emission center wavelengths of 50 nm or more from each other, and the quantum dots include polyethylene glycol-based ligands disposed on a surface thereof. It includes a compound represented by the formula (1-A).

[Formula 1-A]

(In Chemical Formula 1-A,

R 'is represented by the formula 1-1,

[Formula 1-1]

In Chemical Formula 1-1,

R1 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

R2 is represented by the formula 1-2,

[Formula 1-2]

In Chemical Formula 1-2,

A is an oxygen atom or a sulfur atom,

R3 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

), 카르복실산(

), 디티오아세트산(

), 인산(

) 또는 아민(-NH₂)이고,B is mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

) Or amine (-NH ₂ ),

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(-NH₂), 탄소수 1 내지 20의 직쇄 알킬기 또는 탄소수 3 내지 20의 분지쇄 알킬기이고, R “is hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms,

k is an integer from 1 to 100,

l is an integer from 0 to 1,

m is an integer from 0 to 10).

The quantum dots included in the photoconversion resin composition of the present invention are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are characteristic of semiconductors. These quantum dots have the characteristic of emitting energy corresponding to the energy band gap when they reach the excited state from the outside. In short, the photoconversion resin composition of the present invention includes such a quantum dot, so that light conversion into green light and red light is possible through the incident blue light source.

The quantum dot is not particularly limited as long as it can emit light by a stimulus caused by light, but is preferably a cadmium-based compound, for example, a group II-VI semiconductor compound, a group III-V semiconductor compound, a group IV-VI semiconductor compound, and IV. One or more types selected from group elements or compounds containing the same can be used.

The II-VI semiconductor compound may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, and at least one member selected from the group consisting of

The group III-V semiconductor compound may be selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; And one element selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It may be abnormal.

The group IV-VI semiconductor compound may be selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and at least one member selected from the group consisting of an elemental compound selected from the group consisting of a mixture thereof.

The group IV element or the compound containing the same is an element compound selected from the group consisting of Si, Ge, and mixtures thereof; And it may be one or more selected from the group consisting of a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof, but is not limited thereto.

The quantum dots are homogeneous single structures; Dual structures such as core-shell structures, gradient structures, and the like; Or a mixed structure thereof. For example, in the dual structure of the core-shell, the material forming each core and shell may be made of the above-mentioned different semiconductor compounds. More specifically, the core is a binary element selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; And one element selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It may include, but is not limited to, the above materials. The shell may include one or more materials selected from ZnSe, ZnS, and ZnTe, but is not limited thereto.

For example, the quantum dots of the core-shell structure may include InP / ZnS, InP / ZnSe, InP / GaP / ZnS, InP / ZnSe / ZnS, InP / ZnSeTe / ZnS, InP / MnSe / ZnS, and the like.

The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE), but are not limited thereto. .

In the present invention, the quantum dot may be a cadmium-based quantum dot. Specifically, the quantum dot may include a non-cadmium-based quantum dot.

In the present invention, when the quantum dot is a non-cadmium-based quantum dot, it is possible to suppress the risk of environmental pollution, is not harmful to the human body is preferable because there is an advantage that can protect the health of the worker handling it.

The non-cadmium-based quantum dots include two or more quantum dots having different emission center wavelengths, specifically, 50 nm or more, for light conversion to green light and red light by using an incident blue light source. Preferably, the non-cadmium-based quantum dots may include two or more kinds of quantum dots in which the emission center wavelengths differ from each other by 70 nm or more.

When the difference between the emission center wavelengths of the two or more non-cadmium-based quantum dots is within the above range, there is an advantage of providing a display having excellent image quality with wide color reproducibility.

In the non-cadmium-based quantum dot, the quantum dot is effective to realize excellent color reproduction using a green quantum dot having a light emission center wavelength range of 510 nm to 540 nm and a red quantum dot having a light emission center wavelength range of 610 nm to 630 nm. Preferably, the quantum dots may include the green quantum dots and the red quantum dots in the emission center wavelength range, and in this case, by applying quantum dots satisfying each of the emission wavelengths, blue transmitted light of a blue light source, green light emission, red light The use of the color filter of the white light source produced by the light emission is possible, there is an advantage that can provide a display device having a wide color reproduction.

The polyethylene glycol-based ligand is disposed on the surface of the quantum dot by a chemical bond.

Specifically, the quantum dot according to the present invention includes a polyethylene glycol-based ligand comprising a compound represented by the following formula 1-A disposed on the surface. Specifically, the polyethylene glycol ligand is disposed on the surface of the quantum dots by chemical bonds.

[Formula 1-A]

(In Chemical Formula 1-A,

R 'is represented by the formula 1-1,

[Formula 1-1]

In Chemical Formula 1-1,

R1 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

R2 is represented by the formula 1-2,

[Formula 1-2]

In Chemical Formula 1-2,

A is an oxygen atom or a sulfur atom,

R3 is a direct linker or an alkylene group having 1 to 10 carbon atoms,

), 카르복실산(

), 디티오아세트산(

), 인산(

) 또는 아민(-NH₂)이고,B is mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

) Or amine (-NH ₂ ),

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(-NH₂), 탄소수 1 내지 20의 직쇄 알킬기 또는 탄소수 3 내지 20의 분지쇄 알킬기이고, R “is hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms,

k is an integer from 1 to 100,

l is an integer from 0 to 1,

m is an integer from 0 to 10).

In the present invention, the alkyl group may be straight or branched chain, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1- Ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethyl Butyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl , 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present invention, the description of the alkyl group can be applied except that the alkylene group is divalent.

In the present invention, * means a linking group.

The compound represented by Chemical Formula 1-A may be represented by the following Chemical Formula 1-3.

[Formula 1-3]

(In Chemical Formula 1-3,

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(-NH₂), 탄소수 1 내지 20의 직쇄의 알킬기 또는 탄소수 3 내지 20의 분지쇄의 알킬기이고,R "stands for mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms,

o is an integer from 0 to 5,

p is an integer from 0 to 1,

q is an integer from 1 to 50).

Quantum dots containing ligands, such as oleic acid or oleic amine, are well dispersed in high-volatile nonpolar solvents such as hexane and n-hexane, but are typically used for resist manufacturing or display device fabrication. Propylene glycol-based solvents such as propylene glycol methyl ether acetate (PGMEA) are very poor in dispersibility. However, since the quantum dot according to the present invention uses a polyethylene glycol-based ligand, it is easy to disperse in a solvent such as PGMEA, thereby making it easy to work and further protecting the health of the worker. In the case of using the compound represented by Chemical Formula 1-3 as the compound represented by -A, the above-described advantages are particularly maximized.

Specific examples of the polyethylene glycol ligand include 2- (2-methoxyethoxy) acetic acid (2- (2-Methoxyethoxy) acetic acid (WAKO)) and 2- [2- (2-methoxyethoxy). Methoxy] acetic acid (2- [2- (2-Methoxyethoxy) ethoxy] acetic acid (WAKO), succinic acid mono- [2- (2-methoxy-ethoxy) -ethyl] ester (Succinic acid mono- [2] -(2-methoxy-ethoxy) -ethyl] ester, malonic acid mono- [2- (2-methoxy-ethoxy) -ethyl] ester (Malonic acid mono- [2- (2-methoxy-ethoxy)- ethyl] ester, pentanedioic acid mono- {2- [2- (2-ethoxy-ethoxy) -ethoxy] -ethyl} ester (Pentanedioic acid mono- {2- [2- (2-ethoxy-ethoxy) ) -ethoxy] -ethyl} ester), {2- [2- (2-ethyl-hexyloxy) -ethoxy] -ethoxy} -acetic acid ({2- [2- (2-Ethyl-hexyloxy)- ethoxy] -ethoxy} -acetic acid), succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2-ethoxy-ethoxy) -ethoxy] -ethoxy } -Ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester (Succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- ethoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy)- ethoxy] -ethoxy} -ethoxy) -ethyl] ester), succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2- Methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester (Succinic acid mono -[2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester), malonic acid mono- [2- (2- {2- [2- (2- {2- [2- (2-isobutyrate) Methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester (Malonic acid mono- [2- (2- {2- [2- (2- {2- [2- (2-isobutoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester), Hexionate mono- [2- (2 -{2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester (Hexanedioic acid mono- [2- (2- {2- [2- ( 2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester), 2-oxo-hexanedioic acid 6- (2- {2- [2- (2-ethoxy-ethoxy)- Oxy] -ethoxy} -ethyl) ester (2-Oxo-hexanedioic acid 6- (2- {2- [ 2- (2-ethoxy-ethoxy) -ethoxy] -ethoxy} -ethyl) ester), succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- {2 -[2- (2- {2- [2- (2- {2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy } -Ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester (Succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2 -methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester), O- (succinyl) -O'-methylpolyethylene glycol 2'000 (O- (Succinyl) -O'-methylpolyethylene glycol 2'000, Aldrich), (2-butoxy-ethoxy ) -Acetic acid ((2-Butoxy-ethoxy) -acetic acid (WAKO), {2- [2- (carboxymethoxy) ethoxy] ethoxy} acetic acid ({2- [2- (carboxymethoxy) ethoxy] ethoxy } acetic acid, manufactured by WAKO), 2- [2- (benzyloxy) ethoxy] acetic acid (2- [2- (Benzyloxy) ethoxy] acetic acid), (2-carboxymethoxy-ethoxy) -acetic acid (( 2-carbox ymethoxy-ethoxy) -acetic acid, manufactured by WAKO), (2-butoxy-ethoxy) -acetic acid ((2-Butoxy-ethoxy) -acetic acid, manufactured by WAKO), and the like, but are not limited thereto.

The non-cadmium-based quantum dot is a polyethylene glycol ligand, the quantum dot is good to use a solvent such as propylene glycol monomethyl ether acetate used in the color filter production line, not a highly volatile solvent such as toluene, hexane, chloroform Dispersion characteristics can be imparted.

The non-cadmium-based quantum dot including the polyethylene glycol-based ligand may be included in 5% to 150% of the quantum dot, more preferably 10% to 100%. If the content of the non-cadmium-based quantum dot containing the polyethylene glycol-based ligand is less than the above range may be somewhat poor quantum dot dispersion characteristics, if it exceeds the above range, the quantum dot dispersion characteristics are excellent but the curing properties of the coating film is slightly reduced Since it may be, it is preferably included to satisfy the above range.

The quantum dot may be included in 1 to 40 parts by weight, preferably 2 to 20 parts by weight based on 100 parts by weight of the solid content of the light conversion resin composition. When the quantum dots are included in the above range, there is an advantage in that the luminous efficiency is excellent and the reliability of the coating layer is excellent. When the quantum dots are included in the range below the light conversion efficiency of the green light and red light may be insufficient, and when the quantum dot exceeds the above range, the emission of blue light may be relatively lowered, thereby causing a problem of poor color reproducibility.

Binder resin

The photoconversion resin composition according to the present invention includes a binder resin, and the binder resin may include a thermosetting resin or an alkali-soluble resin. Specifically, the binder resin may include an epoxy-containing acrylic binder resin and a cardo-based binder resin as a thermosetting resin or an alkali-soluble resin.

The epoxy-containing acrylic binder resin may include at least one repeating unit of the following Chemical Formulas 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4,

R 4, R 5 and R 6 are each independently hydrogen or a methyl group).

When the epoxy-containing acrylic binder resin including at least one repeating unit of Formulas 2 to 4 is included, the color reproducibility and reliability are excellent due to the excellent light conversion rate and excellent light retention rate of the light conversion resin composition together with excellent mechanical properties. Can lose.

The cardo-based binder resin has reactivity by the action of light or heat and acts as a dispersion medium of quantum dots. The cardo-based binder resin contained in the photoconversion resin composition of the present invention is not limited as long as it acts as a binder resin for quantum dots and can be used as a support for the photoconversion coating layer.

The cardo-based binder resin may include at least one repeating unit of Formula 5 to Formula 10.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 5 to 8,

,

,

,

,

,

,

,

,

,

,

,

또는

이고,X and X 'are each independently a single bond, -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,

Y is an acid anhydride residue,

Z is an acid 2 anhydride residue,

R '''is a hydrogen atom, an ethyl group, a phenyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH = CH ₂ ,

R7, R7 ', R8, R8', R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom or a methyl group,

R13, R13 ', R14 and R14' are each independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, and the alkylene group is an ester bond and a cycloalkylene group having 6 to 14 carbon atoms. And it may be stopped by at least one of arylene groups having 6 to 14 carbon atoms,

R15, R15 ', R16, R16', R17, R17 ', R18 and R18' are each independently a hydrogen atom, a halogen atom or a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms,

r and s are integers satisfying 0 ≦ m ≦ 30 and 0 ≦ n ≦ 30, respectively.

Provided that r and s are not zero at the same time.

[Formula 9]

[Formula 10]

In Chemical Formulas 9 and 10,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

R19 and R20 are each independently hydrogen, hydroxy group, thiol group, amino group, nitro group or halogen atom,

Ar1 is each independently a C6 to C15 aryl group,

Y 'is an acid anhydride residue,

Z 'is an acid 2 anhydride residue,

A 'is O, S, N, Si or Se,

a and b are each independently an integer of 1 to 6,

c and d are each independently an integer of 0 to 30,

Provided that c and d are not zero at the same time.

When the photoconversion resin composition according to the present invention comprises a cardo-based binder resin including at least one repeating unit of the repeating units of the formulas (5) to (10), the inter-process reliability is excellent, and the outgas generation is minimized. There is an advantage that can provide high quality image quality, excellent heat resistance, chemical resistance, durability and reliability with no anti-image after operation and excellent anti-reflection effect.

Y in Chemical Formulas 5 and 7 is a residue of an acid anhydride, and may be obtained by reacting a bisphenol epoxy acrylate compound which is a synthetic intermediate of the cardo-based binder resin of the present invention with an acid anhydride compound. The acid anhydride compound into which the residue Y can be introduced is not particularly limited, and for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylenetetrahydrophthalic anhydride. , Chlororenic acid anhydride, methyltetrahydrophthalic anhydride, and the like.

Z in Chemical Formulas 6 and 8 may be obtained by reacting a bisphenol epoxy acrylate compound which is a synthetic intermediate of the cardo-based binder resin of the present invention with a residue of an acid 2 anhydride. The acid dianhydride compound into which the residue Z can be introduced is not particularly limited, and examples thereof include aromatics such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and bitenyl ether tetracarboxylic dianhydride. And polyhydric carboxylic acid anhydrides.

The 'acid dianhydride' refers to a compound including two acid anhydride groups in a molecule.

In the present invention, the manufacturing method of the cardo-based binder resin is not particularly limited. For example, a bisphenol compound is reacted with an epoxy compound to synthesize a bisphenol epoxy compound, and then a synthesized bisphenol epoxy compound is reacted with an acrylate compound to synthesize a bisphenol epoxy acrylate compound, and then the bisphenol epoxy acrylate compound is an acid anhydride, an acid. It can be prepared by reacting with anhydride or mixtures thereof, but is not limited thereto.

The weight ratio of the cardo-based binder resin to the epoxy-containing acrylic binder resin may be 10:90 to 90:10. When the ratio of the cardo-based binder resin and the epoxy-containing acrylic binder resin is in the above range, the thermal curing property of the coating film is excellent during the post-baking heat treatment process after coating, and the physical properties of the coating film are excellent. The degree of curing may be insufficient and the reliability may be lowered.

The binder resin may be included in an amount of 1 to 40 parts by weight, preferably 1 to 30 parts by weight, and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total photoconversion resin composition. When the binder resin is included in the above range, it is preferable because the heat curing is easy, and the film reduction during heat curing is prevented, so that the coating film properties are good. When the binder resin is included in less than the above range, the film strength may be lowered due to lack of curing degree, and when the binder resin is included in the above range, the coating property may be slightly lowered, thereby making it difficult to form a uniform coating film.

Scattering particles

The light conversion resin composition according to the present invention may include scattering particles.

The scattering particles may use a conventional inorganic material, and preferably include a metal oxide having an average particle diameter of 50 to 1000nm.

Specifically, the metal oxide is Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , One kind selected from the group consisting of SnO, MgO, and combinations thereof is possible. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

However, when the light conversion resin composition according to the present invention includes scattering particles, it is preferable to increase the overall light efficiency in the light conversion coating layer by increasing the path of light emitted from the quantum dots through the scattering particles.

The scattering particles may have an average particle diameter of 50 to 1000nm, preferably use a 100 to 500nm range. In this case, if the particle size is too small, sufficient scattering effect of the light emitted from the quantum dot cannot be expected. On the contrary, if the particle size is too large, the surface of the composition cannot be settled in the composition or the surface of the self-emitting layer of uniform quality can be obtained. Use it.

The scattering particles may include 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the total solids of the light conversion resin composition. When the scattering particles are included in the above range, the effect of increasing the light emission intensity is preferable. When the scattering particles are included in the below range, it may be difficult to secure the emission intensity to be obtained, and when the scattering particles are included in the above range, the transmittance of blue irradiated light may be lowered, which may cause a problem in luminous efficiency. It is preferable to use appropriately.

Thermosetting compounds

The light conversion resin composition according to the present invention may include a thermosetting compound.

It is preferable that it is 20,000 or less, and, as for the average molecular weight of the said thermosetting compound, it is more preferable that it is especially 1,000-20,000. When the average molecular weight of the thermosetting compound satisfies the above conditions, the residual film ratio and heat resistance may be excellent.

The thermosetting compound is based on 100 parts by weight of the total light conversion resin composition It is preferable that it consists of 10-80 weight part of epoxy compounds. When the content of the thermosetting compound is less than the above range, the reliability due to the lack of coating film strength may be lowered.

Specific examples of the thermosetting compound that satisfies the above conditions include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Mixture with (2,3-epoxypropoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and the like. Examples of commercially available products include JER 157S65, 157S70 (trade name; JER Corporation). These can be used individually or in combination of 2 types or more, respectively.

The thermosetting compound according to the present invention may further include an epoxy resin other than the bisphenol A novolac epoxy compound. Preferred examples of the epoxy resin which can be used together with the bisphenol A novolak-type epoxy resin further include, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydrokinone Type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene epoxy resin, phenol noblock type epoxy resin, allocresol noblock type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenol Ethane type epoxy resin, dicyclomethane dienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleus polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy Resin, glyoxal epoxy resin, alicyclic polyfunctional epoxy resin, suit It may be an annular epoxy resin. Each of these epoxy resins may be used alone or in combination with the bisphenol A novolac epoxy resin alone or in combination of two or more thereof.

As said epoxy resin, the following commercial items can be used. More specifically, bisphenol F-type epoxy resins such as YDF-175S (manufactured by Toyo Chemical Co., Ltd.), bisphenol A-type epoxy resins such as YDB-715 (manufactured by Toyo Chemical Co., Ltd.), etc. Biphenyl type epoxy resin such as EPICLON EXA4032 (manufactured by Dainippon Inkyaka Chemical Co., Ltd.) as a naphthalene type epoxy resin, such as YDC-1312 (manufactured by Tosho Chemical Co., Ltd.) as a hydrokinone type epoxy resin, and the like. As a bisphenol A novolak type epoxy resin, such as epicoat YX4000H (made by JER Corporation) as resin, EPPN-201 (Nippon Kayaku (Nippon Kayaku) as a phenol novolak-type epoxy resin, such as JER 157S65 or 157S70 (made by JER Corporation), etc. Product), JER152 154 (JER Co., Ltd.) such as cresol novolac type epoxy resin, EOCN-102S, 103S, 104S or 1020 (manufactured by Nippon Kayaku Co., Ltd.), trishydroxyphenylmethane epoxy resin As epicoat 1032H60 (product of JER Co., Ltd.), trifunctional type As a epoxy resin, VG3101M80 (manufactured by Mitsui Chemical Co., Ltd.), Epicoat 10315 (manufactured by JER Co., Ltd.) as a tetraphenolethane type epoxy resin, ST-3000 (manufactured by Tokyo Chemical Co., Ltd.) as a hydrogenated bisphenol A type epoxy resin, As a glycidyl ester type epoxy resin, Epicoat 190P (manufactured by JER Co., Ltd.), and a glycidylamine type epoxy resin, such as YH-434 (manufactured by Toyo Chemical Co., Ltd.), are used as glyoxal type epoxy resins. As an alicyclic polyfunctional epoxy resin, such as the Chemicals Co., Ltd., Eporide GT-401 (made by Daicel Kagaku Co., Ltd.) etc. is mentioned, The said epoxy resin can be used individually or in combination of 2 or more types, respectively.

The thermosetting compound is preferably 10 to 80% by weight, more preferably 15 to 70% by weight based on 100% by weight of the solid content of the light conversion resin composition. When the thermosetting compound is included within the above range, the residual film ratio and flatness may be good.

Curing accelerator

The light conversion resin composition according to the present invention may include a curing accelerator.

The curing accelerator may be preferably used, for example, at least one compound selected from the group consisting of a carboxylic acid compound, an organic sulfur compound having a thiol group, and an acid generator, but is not limited thereto.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, 1,2,4-benzenetricarboxylic acid anhydride, etc. It may be, but is not limited to such.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like It may be, but is not limited to such.

Specific examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyl Onium salts such as iodonium hexafluoroantimonate, nitrobenzyltosylates, benzointosylates and the like.

The curing accelerator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the light conversion resin composition solids, based on 100 parts by weight of the binder resin and the thermosetting compound. When the content of the curing accelerator satisfies the above range, the photoconversion resin composition comprising the same is highly sensitive, thereby shortening the curing time of the coating film, thus improving productivity and implementing high reliability, and thus forming a coating film The strength and the surface smoothness of the coating portion has an advantage that can be good. On the contrary, when the content of the curing accelerator is included in less than the above range, the decrease in the degree of curing may not be overcome, and wrinkles may occur during the post-process, and when the content exceeds the above range, the light emission characteristics of the photoconversion resin composition may be deteriorated. There is a problem that the luminance is insufficient.

solvent

The light conversion resin composition according to the present invention may contain a solvent.

The solvent contained in the photoconversion resin composition of the present invention may generally include one or two or more kinds, especially when the solvent having a boiling point of 100 to 180 ° C. is contained at least 50% of the total solvent, the flow characteristics are excellent. Since no coating stains and dry foreign matters can be provided, it is possible to provide a good light conversion laminate having no coating foreign matters.

Specific examples may include one or more selected from the group consisting of ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides, and specifically, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, mesitylene, methyl amyl ketone, methyl isobutyl ketone and ethyl 3-ethoxypropionate, 1,3-butylene glycol diacetate, ethyl- From the group consisting of 3-ethoxypropionate, propylene glycol diacetate, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methoxybutyl acetate, ethylene glycol and γ-butyrolactone It may be selected from one type or two or more types.

If the solvent having a boiling point of less than 100 ° C. is more than 50% of the total solvent, the drying speed is high, and staining may occur on the surface of the coating film during the vacuum drying process, while a solvent having a boiling point of more than 180 ° C. is more than 50% of the total solvent. If it is more than%, it may cause a problem in that the time required for the vacuum drying process is long. Therefore, it is appropriate to use a solvent having a boiling point of 100 to 180 ° C. over 50% of the total solvent.

The solvent may be included in 50 to 90% by weight, preferably 60 to 85% by weight relative to 100% by weight of the light conversion resin composition. When the solvent is included in the above range, the coating property may be improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like.

additive

The photoconversion resin composition according to the present invention may further include known additives for various purposes. As such additives, for example, fillers, curing aids, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like can also be used in combination. These additives may be used alone or in combination of two or more, and in consideration of light efficiency and the like, it is preferable to use 1 wt% or less in the total composition.

The filler may be glass, silica, alumina, or the like, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like can be given.

Specifically as said other high molecular compound, curable resin, such as a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, a thermoplastic resin, such as a polyurethane, etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like. Can be mentioned.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The additives can be used by those skilled in the art as appropriate without departing from the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total photoconversion resin composition, but is not limited thereto.

< Light conversion  Laminated Materials>

The light conversion laminated base material which concerns on this invention contains the hardened | cured material of the light conversion resin composition formed on the base material. The photoconversion laminated substrate includes a cured product of the photoconversion resin composition, so that the coating layer forming temperature on the glass substrate can be more effectively processed at 100 to 250 ° C, and may have excellent brightness and long-term reliability compared to existing complex structures. have.

The photoconversion lamination substrate may be silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The photoconversion laminated substrate may be formed by applying and thermosetting the photoconversion resin composition.

<Image display device>

An image display apparatus according to the present invention includes the above-described light conversion laminated substrate. Specifically, the image display device includes a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a mobile terminal such as a mobile phone, and a display for a digital camera. And display devices such as display devices for car navigation systems, and the like, and color display devices are particularly suitable.

The image display apparatus may further include a configuration known to those skilled in the art, except that the image display apparatus is provided with the light conversion multilayer substrate, that is, the present invention is applicable to the light conversion multilayer substrate of the present invention. And an image display device which can be used.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Preparation of Scattering Particle Dispersion

Production Example  1: Preparation of Scattering Particle Dispersion S1

70.0 parts by weight of TiO ₂ (Huntsman TR-88) having a particle diameter of 220 nm as scattering particles, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a dispersant, and 26 parts by weight of propylene glycol methyl ether acetate as a solvent for 12 hours using a bead mill. Scattering particle dispersion S1 was prepared by mixing / dispersing.

Synthesis Example  1: Green Quantum dots  Synthesis (Q-1)

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C, a mixed solution of 0.2 mmol (58 µl) of tris (trimethylsilyl) phosphine (TMS ₃ P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 0.5 minutes.

Then 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the InP core solution synthesized above was added, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP / ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. The precipitate obtained by adding ethanol to the reaction solution cooled to room temperature rapidly and centrifuged was filtered under reduced pressure and dried under reduced pressure to obtain a quantum dot having an InP / ZnSe / ZnS core-shell structure, which was then dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dot is 515 nm, and 5 mL of the quantum dot solution was placed in a centrifuge tube and 20 mL of ethanol was precipitated. The supernatant was discarded by centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots, and 0.50 g of (2-Butoxy-ethoxy) -acetic acid was added thereto, followed by reaction for 1 hour while heating to 60 ° C. under nitrogen atmosphere.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength was 516 nm.

Synthesis Example  2: green Quantum dots  Synthesis (Q-2)

5 mL of the quantum dot chloroform solution synthesized in Synthesis Example 1 was placed in a centrifuge tube and 20 mL of ethanol was precipitated. Discard the supernatant through centrifugation and disperse the quantum dots by adding 2 mL of chloroform to the precipitate, add 0.5 g of O- (Succinyl) -O'-methylpolyethylene glycol 2'000 (Aldrich) and heat to 60 ° C under nitrogen atmosphere. Reacted for one hour.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength was 515 nm.

Synthesis Example  3: Green Quantum dots  Synthesis (Q-3)

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C., a mixed solution of 0.2 mmol (58 μl) of tris (trimethylsilyl) phosphine (TMS3P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 1 minute.

Then 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the InP core solution synthesized above was added, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP / ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. The precipitate obtained by adding ethanol to the reaction solution cooled to room temperature rapidly and centrifuged was filtered under reduced pressure and dried under reduced pressure to obtain a quantum dot having an InP / ZnSe / ZnS core-shell structure, which was then dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dot is 526nm, 5mL of quantum dot solution was placed in a centrifuge tube and 20mL of ethanol was precipitated. The supernatant was discarded by centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots, and 0.50 g of (2-Butoxy-ethoxy) -acetic acid was added thereto, followed by reaction for 1 hour while heating to 60 ° C. under nitrogen atmosphere.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. Maximum emission wavelength was 526 nm.

Synthesis Example  4: Green Quantum dots  Synthesis (Q-4)

5 mL of the quantum dot solution dispersed in chloroform synthesized in Synthesis Example 3 was placed in a centrifuge tube and 20 mL of ethanol was precipitated. Discard the supernatant through centrifugation and disperse the quantum dots by adding 2 mL of chloroform to the precipitate, add 0.5 g of O- (Succinyl) -O'-methylpolyethylene glycol 2'000 (Aldrich) and heat to 60 ° C under nitrogen atmosphere. Reacted for one hour.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength was 525 nm.

Synthesis Example  5: Green Quantum dots Synthesis Example (Q-5)

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C, a mixed solution of 0.2 mmol (58 µl) of tris (trimethylsilyl) phosphine (TMS3P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 1.5 minutes.

Then 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the InP core solution synthesized above was added, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP / ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. The precipitate obtained by adding ethanol to the reaction solution cooled to room temperature rapidly and centrifuged was filtered under reduced pressure and dried under reduced pressure to obtain a quantum dot having an InP / ZnSe / ZnS core-shell structure, which was then dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dot is 526nm, 5mL of quantum dot solution was placed in a centrifuge tube and 20mL of ethanol was precipitated. The supernatant was discarded by centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots. Then, 0.65 g of Carboxy-EG6-undecanethiol (Aldrich) was added thereto and reacted for 1 hour while heating to 60 ° C. under nitrogen atmosphere.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength was 536 nm.

Synthesis Example  6: Green Quantum dots  Synthesis (Q-6)

5 mL of the quantum dot solution dispersed in chloroform synthesized in Synthesis Example 5 was placed in a centrifuge tube and 20 mL of ethanol was precipitated. Discard the supernatant through centrifugation and disperse the quantum dots by adding 2 mL of chloroform to the precipitate, add 0.5 g of O- (Succinyl) -O'-methylpolyethylene glycol 2'000 (Aldrich) and heat to 60 ° C under nitrogen atmosphere. Reacted for one hour.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate the quantum dots, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate was added thereto, followed by dispersion at 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength was 534 nm.

Synthesis Example  7: Red Quantum dots Synthesis Example (Q-7)

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C, a mixture solution of 0.2 mmol (58 µl) of tris (trimethylsilyl) phosphine (TMS ₃ P) and 1.0 mL of trioctylphosphine was injected rapidly, and after 5 minutes, the reaction solution was rapidly cooled to room temperature. Cooled Absorption maximum wavelength 560-590 nm was shown.

2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the InP core solution synthesized above was added thereto, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and then the final mixture was reacted for 2 hours to form an InP / ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. The precipitate obtained by adding ethanol to the reaction solution cooled to room temperature rapidly and centrifuged was filtered under reduced pressure and dried under reduced pressure to obtain a quantum dot having an InP / ZnSe / ZnS core-shell structure, which was then dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dots is 628 nm, and 5 mL of the synthesized quantum dot solution was placed in a centrifuge tube and 20 mL of ethanol was precipitated. Discard the supernatant through centrifugation, disperse the quantum dots by adding 2 mL of chloroform to the precipitate, add 0.65 g of 2- [2- (2-Methoxyethoxy) ethoxy] acetic acid (WAKO), and heat to 60 ° C under nitrogen atmosphere. Reacted for one hour.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to discard the supernatant, and the precipitate was separated. 4 mL of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated and heated to 80 ° C. Solids were adjusted to 25% by PGMEA. Maximum emission wavelength was 628 nm.

Synthesis Example  8: Red Quantum dots  Synthesis (Q-8)

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C, a mixture solution of 0.2 mmol (58 µl) of tris (trimethylsilyl) phosphine (TMS ₃ P) and 1.0 mL of trioctylphosphine was injected rapidly, and after 4.5 minutes, the reaction solution was rapidly cooled to room temperature. Cooled Absorption maximum wavelength 550-585 nm was shown.

2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the InP core solution synthesized above was added thereto, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and then the final mixture was reacted for 2 hours to form an InP / ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was warmed to 280 ° C. 2 mL of the synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. The precipitate obtained by adding ethanol to the reaction solution cooled to room temperature rapidly and centrifuged was filtered under reduced pressure and dried under reduced pressure to obtain a quantum dot having an InP / ZnSe / ZnS core-shell structure, which was then dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dot is 616nm, and 5mL of the synthesized quantum dot solution was placed in a centrifuge tube and 20mL of ethanol was precipitated. Discard the supernatant through centrifugation, disperse the quantum dots by adding 2 mL of chloroform to the precipitate, add 0.65 g of 2- [2- (2-Methoxyethoxy) ethoxy] acetic acid (WAKO), and heat to 60 ° C under nitrogen atmosphere. Reacted for one hour.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to discard the supernatant, and the precipitate was separated. 4 mL of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated and heated to 80 ° C. Solids were adjusted to 25% by PGMEA. Maximum emission wavelength was 616 nm.

Synthesis Example  9: Cardo system  Binder Resin Containing Binder Resin (E-1)

(1) 138 g of 9,9'-bis (4-glysiloxyphenyl) fluorene (Hear chem), acrylic acid 54 g, benzyltriethylammonium chloride (1.4 g) of bisphenol epoxy compound, 1 g of triphenylphosphine (Aldrich Co.), 128 g of propyl glycol methyl ethyl acetate (Daicel Chemical Co.), and 0.5 g of hydroquinone were added thereto, and the mixture was maintained at 120 ° C. for 12 hours, thereby synthesizing a compound represented by the following Formula (11).

(2) 60 g of the compound represented by the following formula (11), 11 g of biphenyltetracarboxylic acid dianhydride (Mitsubishi Gas), 3 g of tetrahydrophthal anhydride (Aldrich), and 20 g of propyl glycol methyl ethyl acetate (Daicel Chemical) , And 0.1 g of N, N'-tetramethylammonium chlorite were added and then maintained at 120 ° C. for 2 hours to synthesize a compound represented by the following Formula 12. The weight average molecular weight of the obtained compound represented by the following formula (12) was 5,400 g / mol. The acid value was 95 mgKOH / g.

[Formula 11]

[Formula 12]

Synthesis Example  10: Cardo system  Binder Resin Containing Binder Resin (E-2)

(1) 4,4 '′-(9H-xanthene-9,9-diyl) diphenol (4,4 ′ ′-(9H-xanthene-9, 364.4 g of 9-diyl) diphenol) and 0.4159 g of t-butylammonium bromide were mixed, and 2359 g of epichlorohydrin was added thereto, followed by heating to 90 ° C. After liquid chromatography, 4,4 ′ ′-(9H-xanthene-9,9-diyl) diphenol was exhausted. Cool to 占 폚 and slowly add 50% aqueous NaOH solution (3 equiv). After epichlorohydrin was completely exhausted by liquid chromatography, the mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled under reduced pressure, and the mixture ratio of dichloromethane and methanol was 50:50. Recrystallized.

Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto and mixed. The temperature was melt | dissolved by heating at 95 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound.

[Formula 13]

(2) After dissolving by adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 13, 78 g of biphenyl tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed up to 4 hours at 110 ° C. Reacted for a while. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize with a cardo-based binder resin. Loss of anhydride was confirmed by IR spectrum. The acid value was 120 mgKOH / g.

Synthesis Example  11: Cardo system  Binder Resin Containing Binder Resin (E-3)

(1) After installing a reflux condenser and thermometer in a three-necked flask, add 42.5 g of 9,9-bisphenolfluorene and 2- (chloromethyl) oxirane. 220 mL was quantified and injected. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90 ° C. while starting stirring. After confirming that the unreactant content is less than 0.3%, the product was distilled under reduced pressure.

After the temperature was lowered to 30 ° C., dichloromethane was injected and NaOH was slowly added thereto. After confirming that the product was 96% or more by high performance liquid chromatography (HPLC) method, 5% HCl was added dropwise to terminate the reaction. After the reaction was extracted and separated, the organic layer was washed with water and washed to be neutral. The organic layer was dried over MgSO ₄ and concentrated by distillation under reduced pressure with a rotary evaporator. Dichloromethane was added to the concentrated product, methanol was added while stirring while raising the temperature to 40 ° C, and the solution temperature was lowered and stirred. The resulting solid was filtered and dried in vacuo at room temperature to give 52.7 g (94% yield) of a white solid powder, the structure of which was confirmed by 1 H NMR.

Scheme 1

1 H NMR in CDCl 3: 7.75 (2H), 7.35-7.254 (6H), 7.08 (4H), 6.74 (4H), 4.13 (2H), 3.89 (2H), 3.30 (2H), 2.87 (2H), 2.71 (2H ).

(2) 3,3 '-(((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1-phenylthio) propan-2-ol) Synthesis of (3,3 '-(((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol)).

After installing a reflux condenser and a thermometer in a three-necked flask, the reaction mixture (1000g), 524g of thiophenol, and 617g of ethanol were added thereto and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC) method, the reaction was terminated. After the reaction was completed, ethanol was removed by distillation under reduced pressure. The organics were dissolved in dichloromethane, washed with water, and then dichloromethane was removed by distillation under reduced pressure. The concentrated organics were dissolved in ethyl acetate and ether ether was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield 64%) of pale yellow oil, and its structure was confirmed by 1 H NMR.

Scheme 2

1 H NMR in CDCl 3: 7.82 (2H), 7.38-6.72 (20H), 6.51 (4H), 4.00 (2H), 3.97 (2H), 3.89 (2H), 3.20 (2H), 3.01 (2H), 2.64 (2H ).

(3) binder resin synthesis

After installing a reflux condenser and a thermometer in a three-necked flask, 3,3 '-(((9H-fluorene-9,9-diyl) bis (4,1-) synthesized in step 2 dissolved in 50% PGMEA solvent. Phenylene)) bis (oxy)) bis (1-phenylthio) propan-2-ol) (3,3 '-(((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) 200 g of bis (oxy)) bis (1- (phenylthio) propan-2-ol)) monomer was added thereto, and the temperature was increased to 115 ° C. 31.1 g of 3,3, '4,4'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-Biphenyltetracarboxylic dianhydride) was added dropwise at 115 ° C, and then maintained at 115 ° C for 6 hours. While stirring. 7.35 g of phthalic anhydride was added thereto, stirred for another 2 hours, and the reaction was terminated. After cooling, a binder resin having a weight average molecular weight of 3,500 g / mol was obtained. The acid value was 150 mg KOH / g.

Synthesis Example  12: binder resin (E-4) containing an epoxy-containing acrylic binder resin

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 18 g of acrylic acid, into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 37.9 g of p-vinyl toluene, 10 g of methyl methacrylate, 34.1 g of glycidyl methacrylate, and 3 g of n-dodecyl mercaptan were added and nitrogen-substituted.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 140 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 13110.

Synthesis Example  13: Binder resin (E-5) containing epoxy containing acrylic binder resin

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 15 g of acrylic acid, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 15.0 g of p-vinyl toluene, 20 g of methyl methacrylate, 50.0 g of glycidyl methacrylate, and 3 g of n-dodecyl mercaptan were added and nitrogen-substituted.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 115 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 13110.

Synthesis Example  14: binder resin (E-6) containing an epoxy-containing acrylic binder resin

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 16 g of acrylic acid, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 14.0 g of p-vinyltoluene, 20 g of methyl methacrylate, 50.0 g of 7-oxabicyclo [4.1.0] heptan-3-ylmethyl acrylate (7-Oxabicyclo [4.1.0] heptan-3-ylmethyl acrylate), 3 g of n-dodecyl mercaptan was added and nitrogen-substituted.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 125 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 11110.

Synthesis Example  15: binder resin (E-7) containing epoxy-containing acrylic binder resin

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 3.5 g of 2,2'-azobisisobutyronitrile, 16 g of acrylic acid in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. , p-vinyltoluene 14.0 g, methyl methacrylate 20 g, glycidyl methacrylate 20.0 g, 7-oxabicyclo [4.1.0] heptan-3-ylmethyl acrylate (7-Oxabicyclo [4.1.0] 20.0 g of heptan-3-ylmethyl acrylate) and 3 g of n-dodecyl mercaptan were added thereto, followed by nitrogen substitution.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 98 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 8090.

Synthesis Example  16: Synthesis of Binder Resin (E-8) Containing Epoxy-Containing Acrylic Binder Resin

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 1.2 g of 2,2'-azobisisobutyronitrile and 16 g of acrylic acid in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. , 14.0 g of p-vinyltoluene, 20 g of methyl methacrylate, 50.0 g of 3-vinyl-7-oxa-bicyclo [4.1.0] heptane, 1.5 g of n-dodecyl mercaptan was added and nitrogen-substituted.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 98 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 18090.

Synthesis Example  17: binder resin (E-9)

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 5 g of acrylic acid, into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 35.0 g of benzyl methacrylate, 60 g of methyl methacrylate, and 3 g of n-dodecyl mercaptan were added thereto, followed by nitrogen substitution.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 40 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 12370.

Synthesis Example  18: binder resin (E-10)

120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of 2,2'-azobisisobutyronitrile, 20 g of acrylic acid, into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 30.0 g of benzyl methacrylate, 50 g of methyl methacrylate, and 3 g of n-dodecyl mercaptan were added and nitrogen-substituted.

After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the binder resin thus synthesized was 160 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 11874.

Light conversion  Preparation of Resin Compositions: Example  1 to 24 and Comparative example  1 to 7

Using the components and contents (% by weight) of Tables 1 to 3, a photoconversion resin composition was prepared according to Examples and Comparative Examples.

Example One 2 3 4 5 6 7 8 9 10 11 12 Quantum dots
Solution ¹⁾ Q-1 8.0 - - - - - 8.0 - - - - - Q-2 8.0 - - - - - 8.0 - - - - Q-3 - - 8.0 - - - - - 8.0 - - - Q-4 - - - 8.0 - - - - - 8.0 - - Q-5 - - - - 8.0 - - - - - 8.0 - Q-6 - - - - - 8.0 - - - - - 8.0 Q-7 0.7 0.7 0.7 0.7 0.7 0.7 - - - - - Q-8 - - - - - - 0.7 0.7 0.7 0.7 0.7 0.7 Q-9 - - - - - - - - - - - - Q-10 - - - - - - - - - - - - spawning
Particles ²⁾ S-1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Thermosetting resin ³⁾ Cardo binder resin E-1 13.6 13.6 - - - - 24.5 2.7 21.8 5.4 - - E-2 - - 13.6 13.6 - - - - - - 21.8 13.6 E-3 - - - - 13.6 13.6 - - - - - - Epoxy-containing acrylic binder resin E-4 13.6 - - - - 13.6 2.7 24.5 - - - - E-5 - 13.6 - - - - - - 5.4 21.8 - - E-6 - - 13.6 - - - - - - 5.4 E-7 - - - 13.6 - - - - - - - 13.6 E-8 - - - - 13.6 - - - - - - - E-9 - - - - - - - - - - - - E-10 - - - - - - - - - - - - Hardening
Accelerator ⁴⁾ G-14) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Solvent ^{5 )} 53.4 53.4 53.4 53.4 53.4 53.4 53.4 53.4 53.4 53.4 53.4 53.4 1) Q-1 to Q-8: Quantum dot dispersions prepared in Synthesis Examples 1 to 8
Q-9: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 560nm, half width 80nm, Aldrich)
Q-10: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 600nm, half width 80nm, Aldrich)
2) Preparation Example 1 Prepared Scattering Particle Dispersion
3) Thermosetting resins prepared in Synthesis Examples 11 to 20
4) 1,2,4-benzenetricarboxylic acid anhydride
5) Propylene Glycol Monomethyl Ether Acetate

Example 13 14 15 16 17 18 19 20 21 22 23 24 Quantum dots
Solution ¹⁾ Q-1 - - - - - 10.0 - - - 12.0 - - Q-2 7.0 - - - - - 10.0 - - - 10.0 - Q-3 - 7.7 - - - - - 10.0 - - - 8.0 Q-4 - - 8.0 - - - - - 10.0 - - - Q-5 - - - 8.0 - - - - - - - Q-6 - - - - 8.0 - - - - - - - Q-7 2.2 - 0.8 - - 1.5 - 1.2 - 2.3 1.2 - Q-8 - 2.2 - 0.8 0.8 - 1.0 - 0.8 - - 0.8 Q-9 - - - - - - - - - - - - Q-10 - - - - - - - - - - - - spawning
Particles ²⁾ S-1 1.0 1.0 1.8 2.0 1.8 0.7 1.4 0.7 1.4 1.0 1.0 1.8 Thermosetting resin ³⁾ Cardo binder resin E-1 - - - - - 21.8 18.5 - - - - 21.8 E-2 5.4 - - - - - - 21.8 5.4 - - - E-3 21.8 15.4 21.8 15.4 - - - - 21.8 5.4 - Epoxy-containing acrylic binder resin E-4 - - - - - - - - - - - - E-5 - - - - - - - - - - - - E-6 21.8 - - - - 13.6 5.4 - - - - 13.6 E-7 - 13.6 15.4 - - - - 5.4 13.6 - E-8 - - - 13.6 15.4 - - - - 5.4 23.6 - E-9 - - - - - - - - - - - - E-10 - - - - - - - - - - - - Hardening
Accelerator ⁴⁾ G-14) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Solvent ^{5 )} 52.6 43.7 48.6 43.8 48.6 42.4 53.7 50.9 58.8 47.5 48.8 44.0 1) Q-1 to Q-8: Quantum dot dispersions prepared in Synthesis Examples 1 to 8
Q-9: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 560nm, half width 80nm, Aldrich)
Q-10: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 600nm, half width 80nm, Aldrich)
2) Preparation Example 1 Prepared Scattering Particle Dispersion
3) Thermosetting resins prepared in Synthesis Examples 11 to 20
4) 1,2,4-benzenetricarboxylic acid anhydride
5) Propylene Glycol Monomethyl Ether Acetate

Comparative example One 2 3 4 5 6 7 Quantum dots
Solution ¹⁾ Q-1 - - - - - 8.0 - Q-2 - - - - - - - Q-3 - - - - - - - Q-4 - - - - - - - Q-5 - - - - - - - Q-6 - - - - - - - Q-7 - - - - - - - Q-8 - - - - - - 0.7 Q-9 8 8 8 8 8 - - Q-10 0.7 0.7 0.7 0.7 0.7 - - spawning
Particles ²⁾ S-1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Thermosetting resin ³⁾ Cardo binder resin E-1 27.2 - 13.6 - - - - E-2 - - - 21.8 5.4 5.4 E-3 - - - - 1.0 - - Epoxy-containing acrylic binder resin E-4 - - - - - - - E-5 - - - - - - - E-6 - - - - - 21.8 21.8 E-7 - - - - - - - E-8 - - - - - - - E-9 - 27.2 13.6 1.0 - - - E-10 - - - 21.8 - - Hardening
Accelerator ⁴⁾ G-14) 10 10 10 10 10 10 10 Solvent ^{5 )} 53.4 53.4 53.4 57.8 57.8 54.1 61.4 1) Q-1 to Q-8: Quantum dot dispersions prepared in Synthesis Examples 1 to 8
Q-9: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 560nm, half width 80nm, Aldrich)
Q-10: InP / ZnS oleylamine ligand toluene solution (luminescence center wavelength 600nm, half width 80nm, Aldrich)
2) Preparation Example 1 Prepared Scattering Particle Dispersion
3) Thermosetting resins prepared in Synthesis Examples 11 to 20
4) 1,2,4-benzenetricarboxylic acid anhydride
5) Propylene Glycol Monomethyl Ether Acetate

Experimental Example

The photoconversion coating layer was prepared using the photoconversion resin compositions prepared in Examples and Comparative Examples as follows, and the brightness, light retention, color reproducibility, heat resistance, and coating film hardness at this time were measured and evaluated. The results are shown in Table 4 below.

(One) Light conversion  Preparation of Coating Layer

The coating film was prepared using the light conversion resin composition prepared in Examples and Comparative Examples. That is, each of the photoconversion resin composition is applied on a 5cm × 5cm glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 10 minutes to form a thin film, followed by 30 minutes in a heating oven at 180 ° C. The light conversion coating layer was prepared by heating. The thickness of the photoconversion resin film prepared above was produced in a thickness of 10 ㎛ depending on the content of the quantum dot.

(2) luminance evaluation

The coating film prepared in (1) was placed on top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree, Inc.), and then measured by using a luminance meter (CAS140CT Spectrometer, Instrument systems, Inc.). The evaluation results are shown in Table 4 below.

(3) Mineral retention

Hard bake the coating substrate produced by the light conversion coating layer manufacturing method at 230 ° C. for 60 minutes to measure the luminous efficiency before hard bake and the luminous efficiency after hard bake and check the level at which luminous efficiency is maintained. , The evaluation results are shown in Table 4 below.

(4) heat resistance evaluation

After forming the coating film in (1), the thickness change due to thermal shock was confirmed by the following equation (1). Specifically, when heat is applied at 230 ° C. for 1 hour to the final finished coating film, the change rate was calculated by the following equation 1 by measuring the thickness before / after applying heat. At this time, when the rate of change of thickness was 90% or more, it was good (○) and bad (×) when less than 90%, and the evaluation results are shown in Table 4 below.

[Equation 1]

Coating shrinkage ratio = {(film thickness after heat treatment) / (film thickness before heat treatment)} × 100 (%).

(5) coating film hardness

Curing degree of the coating film prepared in (1) was measured at a high temperature of 150 ℃ using a hardness tester (HM500; manufactured by Fischer), the surface hardness was evaluated based on the following criteria. The results are shown in Table 2 below.

<Evaluation Criteria>

○: surface hardness of 50 or more

(Triangle | delta): Surface hardness less than 30-50

X: surface hardness less than 30

(6) Color reproducibility

Place the coating film prepared in (1) above the blue light source (XLamp XR-E LED, Royal blue 450, Cree Co., Ltd.), and the red, green, blue patterned color filter substrate (UN65, Samsung TV Color After using the filter, the color coordinates of red, green, and blue were measured by using a colorimeter (OSP-200, Olympus, Inc.). The results are shown in Table 4 below.

Evaluation results Luminance (nit) Mineral retention rate (%) Color reproducibility
(% Of NTSC) Heat resistance
Membrane shrinkage (%) High temperature film hardness
(N / mm2) Example 1 4109 94.3 98.9 93.5 ○ Example 2 4186 92.2 99.1 94.2 ○ Example 3 4069 93.2 98.4 92.3 ○ Example 4 4126 94.9 98.5 94.9 ○ Example 5 4264 90.0 99.0 94.7 ○ Example 6 4016 90.7 97.6 93.0 ○ Example 7 4045 97.6 99.2 95.0 ○ Example 8 4024 91.6 97.7 96.4 ○ Example 9 4018 88.5 96.0 94.3 ○ Example 10 3952 90.6 96.6 95.7 ○ Example 11 4280 90.6 95.6 93.5 ○ Example 12 4206 94.1 97.4 92.2 ○ Example 13 3594 88.1 97.1 95.7 ○ Example 14 3888 94.9 96.8 92.5 ○ Example 15 4148 96.0 96.1 94.6 ○ Example 16 4128 92.8 97.0 92.1 ○ Example 17 4098 93.3 97.0 89.1 ○ Example 18 4195 92.4 98.6 96.0 ○ Example 19 4140 95.1 99.5 92.3 ○ Example 20 4280 93.1 98.5 96.0 ○ Example 21 4206 90.8 95.7 93.8 ○ Example 22 4186 91.1 98.9 93.8 ○ Example 23 4069 90.8 98.6 93.8 ○ Example 24 4126 91.1 98.7 93.8 ○ Comparative Example 1 3533 68.3 63.2 73.1 × Comparative Example 2 2077 42.1 65.1 72.8 × Comparative Example 3 2361 57.5 64.8 74.7 ○ Comparative Example 4 2433 56.8 65.7 77.1 × Comparative Example 5 2077 55.3 62.2 64.5 × Comparative Example 6 3433 85.8 Not measurable 93.2 ○ Comparative Example 7 2077 89.3 Not measurable 93.4 ○

Referring to Table 4, in the case of the embodiment including the cardo-based binder resin and the epoxy-containing acrylic binder resin according to the present invention, the coating film hardness and heat resistance was much better than the comparative example was observed, from these results introduced in the display fabrication It can be seen that the cracking failure of the deposited film generated in the heat treatment step can be greatly reduced.

In addition, the difference in the emission center wavelength of the quantum dot of the embodiment according to the present invention is 50nm or more, when the two or more quantum dots characterized by the green emission wavelength of 510nm ~ 540nm, red emission center wavelength of 610nm ~ 630nm is very excellent color reproducibility However, when one type of quantum dot is used and when the emission center difference is less than 50 nm, it is difficult to apply it as a light source of the color filter due to the lack of performance of color reproducibility. As it is enhanced, it can be seen that the luminance and the light retention rate are significantly superior to the comparative example.

Claims (16)

Two or more kinds of quantum dots whose emission center wavelengths differ by 50 nm or more from each other; And
Including a binder resin,
The binder resin includes a cardo-based binder resin and an epoxy-containing acrylic binder resin,
The quantum dot comprises a polyethylene glycol-based ligand disposed on the surface,
The polyethylene glycol-based ligand is a photo-conversion resin composition, characterized in that it comprises a compound represented by the formula 1-A:
[Formula 1-A]

(In Chemical Formula 1-A,
R 'is represented by the formula 1-1,
[Formula 1-1]

In Chemical Formula 1-1,
R1 is a direct linker or an alkylene group having 1 to 10 carbon atoms,
R2 is represented by the formula 1-2,
[Formula 1-2]

In Chemical Formula 1-2,
A is an oxygen atom or a sulfur atom,
R3 is a direct linker or an alkylene group having 1 to 10 carbon atoms,
B is mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

) Or amine (-NH ₂ ),
R "is a hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms,
k is an integer from 1 to 100,
l is an integer from 0 to 1,
m is an integer from 0 to 10). The method of claim 1,
The compound represented by Formula 1-A is a photo-conversion resin composition, characterized in that represented by the following formula 1-3:
[Formula 1-3]

(In Chemical Formula 1-3,
R "stands for mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), An amine (-NH ₂ ), a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms,
o is an integer from 0 to 5,
p is an integer from 0 to 1,
q is an integer from 1 to 50). The method of claim 1,
The quantum dot is a light conversion resin composition, characterized in that the non-cadmium-based quantum dot. The method of claim 1,
The quantum dot is
Binary elements selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; And one element selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. A core comprising the above materials; And
A light conversion resin composition comprising a; shell comprising at least one material selected from ZnSe, ZnS and ZnTe. The method of claim 1,
The quantum dot is a light conversion resin composition, characterized in that it comprises two or more kinds of quantum dots, the emission center wavelength is different from each other by more than 70nm. The method of claim 5,
The quantum dot is a light conversion resin composition, characterized in that it comprises two or more selected from the group consisting of a green quantum dot having a light emitting center wavelength range of 510nm to 540nm and a red quantum dot of a light emitting center wavelength range of 610nm to 630nm. The method of claim 1,
The polyethylene glycol ligand is 2- (2-methoxyethoxy) acetic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, succinic acid mono- [2- (2-methoxy-ethoxy ) -Ethyl] ester, malonic acid mono- [2- (2-methoxy-ethoxy) -ethyl] ester, pentanedionate mono- {2- [2- (2-ethoxy-ethoxy) -ethoxy ] -Ethyl} ester, {2- [2- (2-ethyl-hexyloxy) -ethoxy] -ethoxy} -acetic acid, succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2-Ethoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester, succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -e Methoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester, malonic acid mono- [2- (2- {2- [2- (2- {2- [ 2- (2-Isobutoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester, hexanediionic acid mono- [2- (2 -{2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -e ) -Ethyl] ester, 2-oxo-hexanedionic acid 6- (2- {2- [2- (2-ethoxy-ethoxy) -ethoxy] -ethoxy} -ethyl) ester, succinic acid mono- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2- {2- [2- (2 -Methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy } -Ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester, (2-butoxy-ethoxy) -acetic acid, carboxy-EG6-undecanethiol and (2-carboxymethoxy-e Methoxy) -acetic acid photo conversion resin composition comprising one or more selected from the group consisting of. The method of claim 1,
The epoxy-containing acrylic binder resin is a photo-conversion resin composition characterized in that it comprises at least one repeating unit of the formula (2) to (4):
[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4,
R 4, R 5 and R 6 are each independently hydrogen or a methyl group). The method of claim 1,
The cardo-based binder resin is a photo-conversion resin composition comprising at least one repeating unit of Formula 5 to Formula 10:
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

(In Chemical Formulas 5 to 8,
X and X 'are each independently a single bond, -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,
Y is an acid anhydride residue,
Z is an acid 2 anhydride residue,
R '''is a hydrogen atom, an ethyl group, a phenyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH = CH ₂ ,
R7, R7 ', R8, R8', R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom or a methyl group,
R13, R13 ', R14 and R14' are each independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, and the alkylene group is an ester bond and a cycloalkylene group having 6 to 14 carbon atoms. And it may be stopped by at least one of arylene groups having 6 to 14 carbon atoms,
R15, R15 ', R16, R16', R17, R17 ', R18 and R18' are each independently a hydrogen atom, a halogen atom or a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms,
r and s are integers satisfying 0 ≦ m ≦ 30 and 0 ≦ n ≦ 30, respectively.
R and s are not zero at the same time.)
[Formula 9]

[Formula 10]

(In Chemical Formulas 9 and 10,
P is each independently

,

,

,

or

ego,
R19 and R20 are each independently hydrogen, hydroxy group, thiol group, amino group, nitro group or halogen atom,
Ar1 is each independently a C6 to C15 aryl group,
Y 'is an acid anhydride residue,
Z 'is an acid 2 anhydride residue,
A 'is O, S, N, Si or Se,
a and b are each independently an integer of 1 to 6,
c and d are each independently an integer of 0 to 30,
Provided that c and d are not zero at the same time.) The method of claim 1,
The weight ratio of the cardo-based binder resin to the epoxy-containing acrylic binder resin is 10:90 to 90:10, the light conversion resin composition. The method of claim 1,
The quantum dot is characterized in that it comprises one or more selected from the group consisting of InP / ZnS, InP / ZnSe, InP / GaP / ZnS, InP / ZnSe / ZnS, InP / ZnSeTe / ZnS and InP / MnSe / ZnS Light conversion resin composition. The method of claim 1,
The light conversion resin composition further comprises at least one selected from the group consisting of scattering particles, a thermosetting compound, a curing accelerator, an additive and a solvent. The method of claim 12,
The scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, A photoconversion resin composition comprising at least one selected from the group consisting of MgO and combinations thereof. The photoconversion laminated base material containing the hardened | cured material of the photoconversion resin composition in any one of Claims 1-13. The method of claim 14,
The light conversion laminated base material whose material of the said light conversion laminated base material is glass. An image display device comprising the light conversion laminated substrate according to claim 15.