KR20190110935A - A light converting resin composition, a light converting laminated substrate and a display device using the same - Google Patents

Abstract

The present invention relates to a light conversion resin composition, which comprises: non-cadmium-based quantum dots including polyethylene glycol-based ligands; scattering particles; alkali-soluble resins; a thermosetting agent; and a solvent, wherein the thermosetting agent includes a polyfunctional alicyclic epoxy resin or a novolac epoxy resin, thereby having excellent coating film surface hardness, elastic recovery rate and adhesion, minimizing outgassing and having excellent dispersibility and optical properties, to a light conversion laminated substrate, and to an image display device using the same.

Description

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

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

In LCD (Liquid Crystal Display) TVs that use a light emitting diode (LED) as a back light unit (BLU), LED BLU is one of the most important parts of 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 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. This does not fall color purity, there is a problem of color reproducibility deteriorated accordingly.

In this regard, Korean Patent No. 10-1690624 discloses a plurality of non-cadmium-based quantum dots dispersed in a polymer resin, and a polymer resin layer having one or both surfaces 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 lower surface of the polymer resin layer is prism patterned or lens patterned, and the lower surface of the polymer resin layer is prism patterned. In this case, the pitch of the prism pattern is 20 to 70 μm, the vertex angle is 95 to 120 °, the cross section of the pattern is a triangle, and the pitch of the lens pattern is 20 to 20 when the lower surface of the polymer resin layer is lens patterned. 70 micrometers, the ratio of pitch to height is 4: 1-10: 1, and the cross section of the said pattern provides the semi-circular optical sheet.

Republic of Korea Patent No. 10-1628065 is a quantum dot; And an aminosiloxane ligand disposed on the surface of the quantum dot and comprising a specific chemical formula.

However, the conventional techniques are not only an optical film having a complex structure such as a barrier layer and a base layer in addition to the light emitting layer including the quantum dots, but also result in a decrease in the luminance of light emitted from the quantum dots. This quenching problem occurs. In addition, the prior art has a problem in long-term reliability as the process proceeds at a low process temperature for processing into an optical film form.

Republic of Korea Patent No. 10-1690624 (2016.12.22. Kolon Industries Co., Ltd.) Republic of Korea Patent No. 10-1628065 (2016.06.01.

The present invention is to solve the above problems, by including a specific thermosetting agent, it is possible to more effectively process the coating layer formation temperature on the glass substrate at 100 to 250 ℃, an image display using the conventional complex optical sheet Compared to the device, the coating film surface hardness, elastic recovery rate, adhesion strength is excellent, and the amount of outgas generation can be minimized, and the light conversion resin composition and the light conversion which improved the excellent dispersibility and optical properties by including the quantum dot which introduces a new ligand It is an object of the present invention to provide a laminated substrate and an image display apparatus using the same.

The optical conversion resin composition according to the present invention for achieving the above object comprises a non-cadmium-based quantum dots, scattering particles, alkali-soluble resin, a thermosetting agent and a solvent containing a polyethylene glycol-based ligand, the thermosetting agent is a polyfunctional alicyclic It is characterized by containing an epoxy resin or novolak epoxy resin.

The photoconversion resin composition according to the present invention includes a specific thermosetting agent, it can effectively process the formation temperature of the coating layer at 100 to 250 ℃, excellent coating surface hardness, elastic recovery rate and adhesion, and minimize the outgas generation amount In addition, by including a quantum dot in which a novel ligand is introduced, the dispersibility and optical properties are excellent.

The light conversion substrate and the image display device using the light conversion laminated substrate made of the light conversion resin composition has a simple structure and excellent 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 a non-cadmium-based quantum dots, scattering particles, an alkali-soluble resin, a thermosetting agent and a solvent containing a polyethylene glycol-based ligand, the thermosetting agent is a polyfunctional alicyclic epoxy resin or novolac epoxy resin By including, the surface hardness, elastic recovery rate and adhesion of the coating film is excellent and can minimize the amount of outgas generated, as well as including a new ligand introduced quantum dot has excellent dispersibility and optical properties.

Quantum dots

Photoconversion resin composition according to the invention is characterized in that it comprises a quantum dot comprising a polyethylene glycol-based ligand.

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 stimulation by light, but more preferably bicadmium. For example, at least one selected from the group III-V semiconductor compound, the group IV-VI semiconductor compound, and the group IV element or a compound containing the same can be used.

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 an isotropic 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.

According to one embodiment of the invention, 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 comprise one or more materials selected from ZnSe, ZnS and ZnTe.

According to one embodiment of the present invention, the quantum dots of the core-shell structure of the present invention are InP / ZnS, InP / ZnSe, InP / GaP / ZnS, InP / ZnSe / ZnS, InP / ZnSeTe / ZnS and InP / MnSe / ZnS It may include one or more selected from the group consisting of. 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. .

The quantum dot of the present invention includes a polyethylene glycol-based ligand disposed on the surface, according to an embodiment of the present invention, the polyethylene glycol-based ligand may include a compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ₁ is represented by the following formula 1-1,

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(

) 또는 탄소수 1 내지 20의 직쇄 알킬기이고,R ₂ is a hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

) Or a straight alkyl group having 1 to 20 carbon atoms,

n is an integer from 2 to 100)

[Formula 1-1]

(In Chemical Formula 1-1,

R ₃ is a direct linker or an alkylene group having 1 to 10 carbon atoms,

R ₄ is represented by the following formula 1-2,

* Means combined hand)

[Formula 1-2]

(In Chemical Formula 1-2,

R ₅ is an oxygen atom or a sulfur atom,

R ₆ is a direct linker or an alkylene group having 1 to 10 carbon atoms,

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(

)으로 이루어진 군으로부터 선택되며,R ₇ is mercapto

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

) Is selected from the group consisting of

m is an integer from 0 to 1, l is an integer from 0 to 10,

* Means combined hand).

Specifically, the compound of Formula 1 may include a compound represented by the following Formula 2.

[Formula 2]

(In Formula 2,

), 카르복실산(

), 디티오아세트산(

), 인산(

), 아민(

), 탄소수 1 내지 20의 직쇄의 알킬기 및 탄소수 3 내지 20의 분지쇄의 알킬기로 이루어진 군으로부터 선택되며,R ₂ is mercapto

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

), A linear alkyl group having 1 to 20 carbon atoms and 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 2 to 50).

As such, when the polyethylene glycol ligand of the present invention includes the compound represented by Chemical Formula 2, dispersibility and optical properties are improved.

In the present invention, an 'alkyl group' may be linear or branched unless otherwise stated, and for example, 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-ethylbutyl, 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.

According to an embodiment of the present invention, the polyethylene glycol ligand is more specifically, 2- (2-methoxyethoxy) acetic acid (2- (2-Methoxyethoxy) acetic acid, WAKO), 2- [2- (2-methoxyethoxy) ethoxy] acetic acid (2- [2- (2-Methoxyethoxy) ethoxy] acetic acid from WAKO), succinic acid mono- [2- (2-methoxy-ethoxy) -ethyl] 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, glutaric 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-ethox y-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]- Methoxy} -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-isobutoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] ester mono- [2- (2- {2- [2- (2- {2- [2- (2-isobutoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl ester), adipic acid 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-adipic acid 6- (2- {2- [2- (2-Ethoxy-ethoxy) -ethoxy] -ethoxy} -ethyl) ester (2-Oxo-hexanedio ic 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} -e Methoxy) -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 Company), (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 (WAKO), 2- [2- (benzyloxy) ethoxy] acetic acid (2- [2- (Benzyloxy) ethoxy] acetic acid), (2- Carboxymethoxy-ethoxy)- It may include ethyl ((2-Butoxy-ethoxy) -acetic acid, WAKO Co.) - Set acid ((2-Carboxymethoxy-ethoxy) -acetic acid, WAKO Co.), (2-butoxy-ethoxy).

As described above, the quantum dot of the present invention includes a polyethylene glycol ligand, so that a solvent such as propylene glycol monomethyl ether acetate, which is used in a color filter production line, is not used as a highly volatile solvent such as toluene, hexane and chloroform. The dispersion characteristic of a quantum dot has a favorable effect.

The photoconversion resin composition of the present invention may further include quantum dots other than the non-cadmium-based quantum dots including the polyethylene glycol-based ligand, in this case, the content of the non-cadmium-based quantum dots including the polyethylene glycol-based ligand is included together. 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total quantum dots containing no ligand. When the non-cadmium-based quantum dot including the polyethylene glycol-based ligand is included in less than the content range, the dispersion properties of the quantum dot may be lowered, and when the non-cadmium quantum dot is included in the content range, the curing property of the coating film may be lowered.

According to one embodiment of the present invention, the quantum dot may include two or more kinds of quantum dots. In the case where the quantum dot includes two or more kinds of quantum dots, there is an advantage in that an image display device having better color reproducibility can be provided.

According to an embodiment of the present invention, the quantum dot may include two or more kinds of quantum dots having different emission center wavelengths for light conversion to green light and red light using the incident blue light source. Specifically, the quantum dot is a green quantum dot having a wavelength range of 510nm to 540nm more effective in implementing color reproducibility; And a red quantum dot having a center wavelength range of 610 nm to 630 nm. In this case, there is a more advantageous advantage in converting blue light into green light or red light.

In this case, the difference in the emission center wavelength of the two or more quantum dots may be 70nm or more. As such, when two or more kinds of quantum dots having different emission center wavelengths are used, color reproducibility can be further improved.

The non-cadmium-based quantum dot of the present invention 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 non-cadmium-based 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 non-cadmium-based quantum dot is less than the above range, the emission of blue light is relatively lowered, which may cause a problem of poor color reproducibility. .

Scattering particles

The light conversion resin composition according to the present invention includes 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.

The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, An oxide including one metal selected from the group consisting of Ce, Ta, In, and combinations thereof is not limited thereto.

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 may be used in the range of 100 to 500nm. 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. Can be used.

The scattering particles may be contained in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total solid 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 range less than the above range it may be difficult to secure the emission intensity to be obtained, if the above range is exceeded because the transmittance of blue irradiation light is significantly lowered may cause problems in color reproducibility, within the above range It is preferable to use suitably.

Alkali soluble resin

The photoconversion resin composition according to the present invention comprises an alkali-soluble resin.

The alkali-soluble resin can be selected from a variety of polymers used in the application art. The alkali-soluble resin is not particularly limited as long as it contains an acid value or a hydroxyl group, but epoxy (meth) acrylate resins, acrylic resins, and carboxyl groups are contained in terms of shape and pattern level, adhesion to the substrate, and solvent resistance (alicyclic). Epoxy mechanical resins, novolak-based resins, polyvinylphenol-based resins, etc. may be mentioned. Among them, epoxy (meth) acrylate resins and (alicyclic) epoxy machine resins may be more effective. The binder resin containing the (alicyclic) epoxy group is more preferable because it can improve the reliability such as chemical resistance and electrical properties while having little change over time.

In addition, the molecular weight of the alkali-soluble resin is preferably in the range of the weight average molecular weight of 3,000 to 40,000, more preferably in the range of 5,000 to 20,000 may be good. When the molecular weight of the alkali-soluble resin is within the above range, there is a tendency that the balance between film forming ability, reliability and developability is excellent. In addition, the acid value of the alkali-soluble resin is preferably in the range of 50 to 200 mg · KOH / g based on solid content, and when the acid value of the binder resin is within the above range, developability against alkali development is excellent and residues are generated. This is suppressed and there exists an advantage that the adhesiveness of a pattern improves.

In the present invention, "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can be obtained by titration using an aqueous potassium hydroxide solution.

The alkali-soluble resin may be included in 1 to 80 parts by weight, preferably 5 to 70 parts by weight, more preferably 2 to 70 parts by weight based on 100 parts by weight of the total photoconversion resin composition.

When the alkali-soluble resin is included in the above range, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable. If the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.

Thermosetting agent

The photoconversion resin composition according to the present invention contains a thermosetting agent.

The thermosetting agent is not only excellent in the surface hardness and adhesion of the coating film, it is also excellent in the elastic recovery rate in the high temperature process, there is an advantage in the afterimage that can occur when operating the panel by minimizing the amount of outgas (outgas).

The thermosetting agent of the present invention is characterized in that it comprises a polyfunctional alicyclic epoxy resin or a novolak epoxy resin, which is advantageous in securing time stability, especially when using a silane-modified epoxy resin.

According to one embodiment of the present invention, the multifunctional alicyclic epoxy resin may include a compound represented by the following Chemical Formula 3 or 4.

 [Formula 3]

(In Chemical Formula 3,

R ₈ is a C1 to C10 alkyl group,

a, b and c are each independently an integer from 1 to 20).

 [Formula 4]

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.

Commercially available products of the polyfunctional alicyclic epoxy resin include "CEL-2021" by Daicel Chemical Industries, Ltd., alicyclic solid epoxy resin "EHPE-3150", epoxidized polybutadiene "PB3600", and flexible alicyclic epoxy The compound "CEL-2081", a lactone modified epoxy resin "PCL-G", etc. can be used. In addition, Daicel Kagaku Kogyo Co., Ltd. "Ceroxide 2000", "Epolyd GT-3000", "GT-4000", etc. can be used, but it is not limited to this.

By using the polyfunctional cycloaliphatic epoxy resin, not only the surface hardness and adhesion of the coating film are excellent, but also the elastic recovery rate at a high temperature process is excellent, and afterimages may occur when operating the panel by minimizing the amount of outgas. There are beneficial benefits to this.

According to one embodiment of the present invention, the novolac epoxy resin may include a compound represented by the following Formula 5.

[Formula 5]

(In Chemical Formula 5,

v is an integer from 1 to 20).

A commercial product of the novolac epoxy resin may be used, such as Sumi epoxy ESCN 195XL (manufactured by Sumitomo Kagaku Kogyo Co., Ltd.), but is not limited thereto.

By using the novolac epoxy resin, not only the surface hardness and adhesion of the coating film is excellent, but also the elastic recovery rate in the high temperature process is excellent, and the amount of outgas is minimized, which is beneficial to the afterimage that may occur when operating the panel. There is an advantage.

The thermosetting agent may be included in an amount of 0.1 to 40% by weight, preferably 0.5 to 35% by weight, and more preferably 5 to 30% by weight, based on 100% by weight of the light conversion resin composition solids.

When the thermosetting agent satisfies the above range, the hardness of the coating film is improved, so that the coating film surface hardness and adhesion are excellent, as well as the elastic recovery rate at a high temperature process, and the amount of outgas generated can be minimized when operating the panel. There is a beneficial advantage to afterimages. On the other hand, when the thermosetting agent is out of the range, the surface hardness of the coating film may be lowered, the adhesion may be lowered, and cracks may occur, and the elastic recovery rate at the high temperature process may be lowered, thereby causing surface wrinkles. There is this. In addition, if the amount of outgas is increased, there is a risk of image retention when the panel is operated.

solvent

The photoconversion resin composition which concerns on this invention contains a solvent.

The solvent may include at least one or more, in particular, when the solvent having a boiling point of 100 to 240 ℃ 50% or more compared to the total solvent, the flow characteristics are excellent, coating stains and dry foreign matter does not occur, the coating is It is possible to provide a good light conversion laminated substrate free of water.

When 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 240 ° C. is 50% of the total solvent. If it is more than%, it may cause a problem in that the tack-time is long in the vacuum drying process. Therefore, it is appropriate to use a solvent having a boiling point of 100 to 240 ° C. that is at least 50% of the total solvent.

Specific examples of the solvent may include one or more selected from the group consisting of ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like, specifically propylene glycol monomethyl ether acetate, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, mesitylene, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, butanol, hexanol, cyclohexanol And ethyl 3-ethoxypropionate, 1,3-butylene glycol diacetate, ethyl-3-ethoxy propionate, propylene glycol diacetate, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl Ether, methoxybutyl acetate, ethylene glycol and γ-butyrolactone Emitter may be at least one or two more selected.

The content of the solvent in the photoconversion resin composition of the present invention may be included in 5 to 90% by weight, preferably 30 to 80% by weight relative to 100% by weight of the photoconversion 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.

<Optical conversion laminated substrate>

The light conversion laminated base material which concerns on this invention contains the hardened | cured material of a light conversion resin composition. Since the light conversion laminated substrate includes a cured product of the light conversion resin composition, when the coating layer is formed on the substrate, the light conversion laminate may be processed more effectively at a temperature of 100 to 250 ° C., and luminance and long-term reliability may be higher than those of a conventional complex structure. Can be excellent.

The substrate may be glass, 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 the photoconversion resin composition on the above-described substrate and exposing, developing and thermosetting in a predetermined pattern.

<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

Preparation Example 1 Preparation of Scattering Particle Dispersion S-1

70.0 parts by weight of TiO ₂ (Huntsman TTO-55 (C)) having a particle diameter of 150 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 Scattering particle dispersion S-1 was prepared by mixing / dispersing for 12 hours.

Synthesis Example 1 Synthesis of Quantum Dots

Synthesis Example 1-1: Synthesis of Green Quantum Dots (A-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 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 mixed 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 InP / ZnSe core shell synthesized above 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 of 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 was 515 nm, and 5 mL of the quantum dot solution was placed in a centrifuge tube and 20 mL of ethanol was precipitated. Discard the supernatant separated by centrifugation, add 2 mL of chloroform to the precipitate to disperse the quantum dots, add 0.5 g of O- (Succinyl) -O'-methylpolyethylene glycol 2'000 (Aldrich) and place it under nitrogen The reaction was carried out for 1 hour while heating to.

Subsequently, 25 mL of n-hexane was added to the obtained reactant to precipitate a quantum dot, followed by centrifugation to separate the precipitate, and 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added thereto, and the mixture was heated and heated to 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission peak of the finally obtained quantum dot was 515 nm.

Synthesis Example 1-2: Synthesis of Green Quantum Dots (A-2)

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 mixed solution synthesized above was added thereto, 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 InP / ZnSe core-shell synthesized above 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 was 526 nm, and 5 mL of the quantum dot solution was placed in a centrifuge tube and 20 mL of ethanol was precipitated. The supernatant separated by centrifugation was discarded and quantum dots were dispersed by adding 2 mL of chloroform to the precipitate, and 0.50 g of (2-Butoxy-ethoxy) -acetic acid was added thereto, and the mixture was reacted for 1 hour while heating to 60 ° C. under a nitrogen atmosphere.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate a quantum dot, followed by centrifugation to separate the precipitate. 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added thereto, and the mixture was heated and heated to 80 ° C. Solids were adjusted to 25% by PGMEA. The maximum emission wavelength of the finally obtained quantum dot was 536 nm.

Synthesis Example 1-3 Synthesis of Red Quantum Dots (A-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 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

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 mixed solution synthesized above was added thereto, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and 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 / ZnSe core-shells were 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 was 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 separated by centrifugation, add 2 mL of chloroform to the precipitate to disperse the quantum dots, add 0.65 g of 2- [2- (2-Methoxyethoxy) ethoxy] acetic acid (WAKO), and under 60 ° C under nitrogen atmosphere. The reaction was carried out for 1 hour while heating to.

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to discard the supernatant. . At this time, the solid content was adjusted to 25% by PGMEA. The maximum emission wavelength of the finally obtained quantum dot was 628 nm.

Synthesis Example 1-4: Red Quantum Dot Synthesis (A-4)

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

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 mixed solution synthesized above was added thereto, followed by 4.8 mmol of selenium (Se / TOP) in trioctylphosphine, and 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 InP / ZnSe core-shell synthesized above 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 peak emission peak of the photoluminescence spectrum of the obtained nano quantum dot is 616nm, 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. . At this time, the solids were adjusted to 25% by PGMEA. The maximum emission wavelength of the finally obtained quantum dot was 616 nm.

Synthesis Example 2 Alkali Soluble Resin (C)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were added thereto, stirred and mixed to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanethiol. 24 parts by weight of PGMEA was added thereto, followed by stirring and mixing to prepare a lot of chain transfer agent dropwise. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. The ring started. Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask, followed by 8 hours at 110 ° C. The reaction was continued and an alkali-soluble resin having a solid content of 29.1 wt%, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g was then cooled to room temperature.

Examples 1-12 and Comparative Examples 1-14: Preparation of Photoconversion Resin Composition

To use the components and contents (% by weight) of Table 1 to prepare a light conversion resin composition according to the Examples and Comparative Examples.

Quantum dots Scattering particles Alkali soluble resin Thermosetting agent solvent A-1 A-2 A-3 A-4 A-5 A-6 S-1 C D-1 D-2 D-3 E Example 1 8.0 - 0.7 - - - 0.7 27.2 9.32 9.32 - 44.76 Example 2 8.0 - - 0.7 - - 0.7 27.2 9.32 9.32 - 44.76 Example 3 - 8.0 0.7 - - - 0.7 27.2 9.32 9.32 - 44.76 Example 4 - 8.0 - 0.7 - - 0.7 27.2 9.32 9.32 - 44.76 Example 5 8.0 - 0.7 - - - 0.7 27.2 2.33 - - 61.07 Example 6 8.0 - - 0.7 - - 0.7 27.2 6.21 12.43 - 44.76 Example 7 8.0 - 0.7 - - - 0.7 27.2 12.43 6.21 - 44.76 Example 8 8.0 - - 0.7 - - 0.7 27.2 18.64 - - 44.76 Example 9 - 8.0 0.7 - - - 0.7 27.2 2.33 - - 61.07 Example 10 - 8.0 - 0.7 - - 0.7 27.2 6.21 12.43 - 44.76 Example 11 - 8.0 0.7 - - - 0.7 27.2 12.43 6.21 - 44.76 Example 12 - 8.0 - 0.7 - - 0.7 27.2 18.64 - - 44.76 Comparative Example 1 8.0 - - - 0.7 - 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 2 8.0 - - - - 0.7 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 3 - 8.0 - - 0.7 - 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 4 - 8.0 - - - 0.7 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 5 8.0 - - - 0.7 - 0.7 27.2 9.32 - 9.32 44.76 Comparative Example 6 8.0 - - - - 0.7 0.7 27.2 9.32 - 9.32 44.76 Comparative Example 7 - 8.0 - - 0.7 - 0.7 27.2 9.32 - 9.32 44.76 Comparative Example 8 - 8.0 - - - 0.7 0.7 27.2 9.32 - 9.32 44.76 Comparative Example 9 - - - - 5.4 3.3 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 10 - - - - 4.8 3.9 0.7 27.2 9.32 9.32 - 44.76 Comparative Example 11 8.0 - 0.7 - - - 0.7 27.2 - - 10.49 52.92 Comparative Example 12 8.0 - 0.7 - - - 0.7 27.2 9.32 - 9.32 44.76 Comparative Example 13 8.0 - 0.7 - - - 0.7 27.2 - 9.32 9.32 44.76 Comparative Example 14 8.0 - 0.7 - - - 0.7 27.2 - - - 63.4 A-1: QD of Synthesis Example 1-1
A-2: QD of Synthesis Example 1-2
A-3: QD of Synthesis Example 1-3
A-4: QD of Synthesis Example 1-4
A-5: InP / ZnS olelyamine ligand toluene solution (luminescence center wavelength 560nm, half width 80nm, Aldrich)
A-6: InP / ZnS olelyamine ligand toluene solution (luminescence center wavelength 590nm, half width 80nm, Aldrich)
S-1: Scattering Particles of Preparation Example 1
C: alkali-soluble resin of Synthesis Example 2
D-1: CEL-2021 (made by Daicel Chemical Industries, Ltd.)
D-2: Sumi epoxy ESCN 195XL (manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)
D-3: Composelan E-101 (manufactured by Arakawa Chemical Industry Co., Ltd.)
E: Propylene Glycol Monomethyl Ether Acetate
* For the comparative example, the toluene solvent contained in the ligand was removed under reduced pressure, and then propylene glycol monomethyl ether acetate was replenished by the amount of the toluene solvent removed.

Experimental Example

The photoconversion coating layer was prepared using the photoconversion resin compositions prepared in Examples and Comparative Examples as follows, and the coating film brightness, color reproducibility, surface hardness, elastic recovery rate, adhesion, outgas generation amount, and change rate over time Was measured in the same manner as described below, and the results are shown in Table 2 below.

(One) Light conversion  Coating layer manufacturing

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 method, then placed on a heating plate and maintained at a temperature of 100 ℃ for 10 minutes to form a thin film and then in a heating oven at 180 ℃ for 30 minutes The light conversion coating layer was prepared by heating. The thickness of the photoconversion resin film prepared above was produced in a thickness of 8.0 ㎛ depending on the content of the quantum dot.

(2) luminance

The coating film prepared in (1) was placed on top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree Co., Ltd.), and then measured by using a luminance meter (CAS140CT Spectrometer, Instrument systems Co., Ltd.) to measure the brightness of blue light. Was measured, and the evaluation results are shown in Table 2 below.

(3) Color reproducibility

The coating film prepared in (1) is placed on the blue light source (XLamp XR-E LED, Royal blue 450, Cree Co., Ltd.), and the red, green and 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 2 below.

(4) coating film surface hardness

The degree of cure of the coating film prepared in (1) was measured at 150 ° C. using a hardness tester (HM500; manufactured by Fischer). The results obtained at this time are shown in Table 2 below. At this time, the coating film surface hardness was evaluated based on the following criteria.

<Evaluation Criteria>

○: surface hardness of 50 or more

(Triangle | delta): Surface hardness 30 or more and less than 50

X: surface hardness less than 30

(5) Elastic recovery

The elastic recovery rate of the coating film prepared in (1) was used by Fisher hardness meter (fisherscope HM-2000, fisher, Inc.), measured by applying a force up to 50mN to the coating film prepared in (1) and the results are shown in Table 2 below Indicated.

<Evaluation Criteria>

○: excellent, elastic recovery rate 60 or more

△: insufficient, elastic recovery rate 30 to less than 60

×: deterioration, elastic recovery rate less than 30

(6) adhesion

The adhesion evaluation of the coating film prepared in (1) was carried out using a TQC's Cross Cut Adhesion Test CC1000 to cut a total of 100 grids by drawing 11 lines in the horizontal and vertical directions at 1 mm intervals on the surface. , TQC Tape was used to evaluate the adhesion of the cut surface. At this time, the adhesion was evaluated by the following criteria and the results obtained are shown in Table 2 below.

<Evaluation Criteria>

○: keep more than 90 patterns

(Triangle | delta): 60-89 patterns hold

×: retains 9 to 59 patterns

(7) outgas ( outgas ) Amount

The collected compound was analyzed by pyrolyzing the coating layer prepared in (1) at 230 ° C. through Py-GC / FID for 30 minutes.

At this time, the outgas generation amount was evaluated based on the following criteria, the results obtained are shown in Table 2 below.

<Evaluation Criteria>

The value of Comparative Example 1 was expressed as a percentage based on 100%, and the lower the value, the better.

( 8) Rate of change over time

For the preparation of the coating layer of (1), by measuring the viscosity after storage for one month at room temperature and the initial viscosity of the prepared photoconversion resin composition was confirmed whether the change over time. It measured on the conditions of 50 rpm of rotation speed in 25 degreeC using the viscometer (The TV-35 viscometer by the Kyocera Co., Ltd.).

At this time, the rate of change over time was evaluated by the following criteria, the results obtained are shown in Table 2 below.

<Evaluation Criteria>

Viscosity change rate at room temperature was based on within 102%, and less than 102% was shown to have stability over time.

[Viscosity change rate of light conversion resin composition] = (time-viscosity / initial viscosity) Х100

(9) Haze

Haze was measured using a haze meter (HZ-1, manufactured by Suga) for the light conversion resin composition containing no scattering particles in Examples and Comparative Examples, and the results obtained are shown in Table 2 below. It was.

<Evaluation Criteria>

The haze value is 8.0 or less in a favorable level.

Luminance
(nit) Color reproducibility
(% Of NTSC) Coating hardness Shout
Recovery rate Adhesion Outgas
(%) Haze Change over time
(% After 1 month) Example 1 3867 98.7 ○ ○ ○ 14 1.2 100.3 Example 2 3913 99.2 ○ ○ ○ 12 0.9 100.5 Example 3 3835 99.6 ○ ○ ○ 11 0.8 100.2 Example 4 3920 99.5 ○ ○ ○ 16 1.0 100.3 Example 5 3880 98.8 ○ ○ ○ 13 1.1 100.1 Example 6 3864 98.8 ○ ○ ○ 11 1.2 100.1 Example 7 3890 98.9 ○ ○ ○ 10 1.1 100.2 Example 8 3888 98.9 ○ ○ ○ 12 1.3 100.2 Example 9 3856 99.2 ○ ○ ○ 10 1.2 100.3 Example 10 3912 99.2 ○ ○ ○ 11 1.0 100.3 Example 11 3846 99.1 ○ ○ ○ 12 1.1 100.2 Example 12 3913 99.1 ○ ○ ○ 13 0.9 100.1 Comparative Example 1 2423 65.2 ○ ○ ○ 16 8.7 110.0 Comparative Example 2 2510 64.3 ○ ○ ○ 15 11.3 115.4 Comparative Example 3 2362 64.1 ○ ○ ○ 14 12.1 113.0 Comparative Example 4 2371 62.2 ○ ○ ○ 17 16 114.8 Comparative Example 5 1921 56.3 ○ ○ ○ 13 22 150.3 Comparative Example 6 1832 55.1 ○ ○ ○ 16 21 149.5 Comparative Example 7 1853 54.3 ○ ○ ○ 15 19 143.6 Comparative Example 8 1735 52.1 ○ ○ ○ 17 22 147.2 Comparative Example 9 2016 63.1 ○ ○ ○ 11 18.3 123.0 Comparative Example 10 2100 62.2 ○ ○ ○ 13 13.1 120.2 Comparative Example 11 1823 60.1 ○ ○ ○ 15 23 146.2 Comparative Example 12 2410 66.2 ○ ○ ○ 16 12.1 130.3 Comparative Example 13 2365 59.3 ○ ○ ○ 13 15.3 128.2 Comparative Example 14 3915 98.4 × × × 190 1.2 100.3

Referring to Table 2, in the case of Examples 1 to 12 that satisfies all the configurations proposed in the present invention, the luminance, color reproducibility than the case of Comparative Examples 1 to 14 that do not satisfy any of the configurations presented in the present invention In addition to the optical properties such as haze, as well as coating film hardness, elastic recovery rate, adhesion, outgas generation prevention, it was confirmed that the more excellent effect in terms of change rate over time.

Specifically, in Comparative Examples 1 to 10, which do not satisfy the configuration of the quantum dots presented in the present invention, the liquid phase dispersibility is poor and the quantum efficiency of the quantum dots is lowered, thereby decreasing the brightness and color reproducibility, and increasing the haze. It was confirmed that the characteristics were not good, and in Comparative Examples 5 to 8 and Comparative Examples 11 to 13 including the silane-modified epoxy resin as the thermosetting agent, it was confirmed that the change with time was not good. In particular, in the case of Comparative Example 14 that does not contain a thermosetting agent at all, it was confirmed that the coating film hardness, elastic recovery rate, adhesion strength is not all good.

Claims (15)

A cadmium-based quantum dot including a polyethylene glycol-based ligand, scattering particles, an alkali-soluble resin, a thermosetting agent and a solvent,
The thermosetting agent is a light conversion resin composition comprising a polyfunctional alicyclic epoxy resin or novolac epoxy resin. The method of claim 1,
The polyethylene glycol-based ligand is a photo-conversion resin composition comprising a compound represented by the following formula (1):
[Formula 1]

(In Formula 1,
R ₁ is represented by the following formula 1-1,
R ₂ is a hydrogen atom, mercapto (

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

) Or a straight alkyl group having 1 to 20 carbon atoms,
n is an integer from 2 to 100)
[Formula 1-1]

(In Chemical Formula 1-1,
R ₃ is a direct linker or an alkylene group having 1 to 10 carbon atoms,
R ₄ is represented by the following formula 1-2,
* Means combined hand)
[Formula 1-2]

(In Chemical Formula 1-2,
R ₅ is an oxygen atom or a sulfur atom,
R ₆ is a direct linker or an alkylene group having 1 to 10 carbon atoms,
R ₇ is mercapto

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

) Is selected from the group consisting of
m is an integer from 0 to 1, l is an integer from 0 to 10,
* Means combined hand). The method of claim 1,
The quantum dot is a light conversion resin composition, characterized in that it comprises two or more quantum dots. The method of claim 2,
The compound of Formula 1 is a photo-conversion resin composition comprising a compound represented by the following formula (2):
[Formula 2]

(In Formula 2,
R ₂ is mercapto

), Carboxylic acid (

), Dithioacetic acid (

), Phosphoric acid (

), Amine (

), A linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms,
o is an integer of 0-5, p is an integer of 0-1, q is an integer of 2-50). The method of claim 1,
The polyfunctional alicyclic epoxy resin is a light conversion resin composition comprising a compound represented by the following formula (3) or (4):
[Formula 3]

(In Chemical Formula 3,
R ₈ is a C1 to C10 alkyl group,
a, b and c are each independently an integer from 1 to 20).
[Formula 4]

The method of claim 1,
The novolac epoxy resin is a photo-conversion resin composition comprising a compound represented by the following formula (5):
[Formula 5]

(In Chemical Formula 5,
v is an integer from 1 to 20). The method of claim 1,
The thermosetting agent is a light conversion resin composition, characterized in that contained in 0.1 to 40% by weight based on 100% by weight of the total solid content of the light conversion resin composition comprising the same. 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 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 3,
The quantum dot is a green quantum dot of the emission center wavelength range of 510nm to 540nm; And a red quantum dot having a light emission center wavelength of 610 nm to 630 nm. The method of claim 10,
The quantum dot is a light conversion resin composition, characterized in that it comprises at least two kinds of quantum dots, the emission center wavelength is 70nm or more different from each other. The method of claim 1,
The polyethylene glycol ligand is 2- (2-methoxyethoxy) acetic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, monosuccinate mono- [2- (2-methoxy-ethoxy ) -Ethyl] ester, mono malonic acid- [2- (2-methoxy-ethoxy) -ethyl] ester, mono glutarate- {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, adipic acid mono- [2- (2 -{2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethyl] , 2-oxo-adipic 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-) Methoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -Ethoxy] -ethoxy} -ethoxy) -ethyl] ester, O- (succinyl) -O'-methylpolyethylene glycol 2'000, (2-butoxy-ethoxy) -acetic acid, carboxy-EG6- An optical conversion resin composition comprising one or more selected from the group consisting of undecanethiol and (2-carboxymethoxy-ethoxy) -acetic acid. The method of claim 1,
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. A photoconversion laminated substrate comprising a cured product of the photoconversion resin composition according to any one of claims 1 to 13. An image display device comprising the light conversion laminated substrate according to claim 14.