KR102237547B1 - A light converting resin composition, a light converting laminated substrate and a display device using the same - Google Patents

Abstract

The present invention comprises a non-cadmium-based quantum dot containing a polyethylene glycol-based ligand, scattering particles, an alkali-soluble resin, a thermal curing agent and a solvent, and the thermal curing agent includes a polyfunctional alicyclic epoxy resin or a novolac epoxy resin. The present invention relates to a photo-conversion resin composition, a photo-conversion laminate material, and an image display device using the same, excellent in surface hardness, elastic recovery rate, and adhesion, and not only can minimize the amount of outgassing, but also have excellent dispersibility and optical properties.

Description

A light conversion resin composition, a light conversion laminate, and an 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 photo-conversion resin composition, a photo-conversion laminate, and an image display device using the same.

In LCD (Liquid Crystal Display) TVs that use Light Emitting Diode (LED) as a backlight unit (BLU), LED BLU is one of the most important parts of an LCD TV as the part that actually emits light.

As a method of forming a white LED BLU, a white LED BLU is formed by combining a red (Red, R), green (Green, G) and blue (Blue, B) LED chip, or a blue LED chip and a wide half width. White is realized by using a combination of yellow (Y) phosphors with a light emission wavelength of.

However, in the case of combining red, green, and blue LED chips, there is a problem of high manufacturing cost depending on the number of LED chips and the complicated process, and when combining a yellow phosphor with a blue LED chip, the wavelength division of green and red This does not result in a decrease in color purity, and there is a problem in that color reproducibility decreases accordingly.

In this regard, Korean Patent Registration No. 10-1690624 discloses a polymer resin layer in which a plurality of non-cadmium-based quantum dots are dispersed in a polymer resin, and one or both sides are 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 a lower surface of the polymer resin layer is a prism patterned or lens patterned, and a lower surface of the polymer resin layer is a prism patterned In case the pitch of the prism pattern is 20 to 70 μm, the apex angle is 95 to 120°, the cross section of the pattern is triangular, and the lower surface of the polymer resin layer is a lens pattern, the pitch of the lens pattern is 20 to 70㎛, the ratio of the pitch to the height is 4: 1 to 10: 1, and the cross section of the pattern is provided with a semicircular optical sheet.

Republic of Korea Patent Registration No. 10-1628065 is a quantum dot; And it is disposed on the surface of the quantum dot, it provides a light-emitting complex comprising an aminosiloxane-based ligand represented by a specific formula.

However, the prior art is 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 decreases the luminance of the quantum dots accordingly, and when the film is produced at too high a temperature during the manufacturing process, the quantum dots This quenching problem occurs. In addition, the prior art has a problem in long-term reliability as it proceeds at a low process temperature in order to process it into an optical film form.

Korean Patent Registration No. 10-1690624 (2016.12.22. Kolon Industries Co., Ltd.) Korean Patent Registration No. 10-1628065 (2016.06.01. LMS Co., Ltd.)

The present invention is to solve the above problems, by including a specific heat curing agent, it is possible to more effectively process the coating layer formation temperature on the glass substrate at 100 to 250 ℃, and image display using an existing optical sheet of a complex structure Compared to the device, the coating film surface hardness, elastic recovery rate, and adhesion are superior, and the amount of outgas is minimized, and by including quantum dots incorporating a new ligand, excellent dispersibility and optical properties are improved, photoconversion resin composition. An object thereof is to provide a laminated substrate and an image display device using the same.

The photo-conversion resin composition according to the present invention for achieving the above object comprises non-cadmium-based quantum dots including polyethylene glycol-based ligands, scattering particles, alkali-soluble resin, a thermal curing agent and a solvent, and the thermal curing agent is a polyfunctional alicyclic It characterized in that it comprises an epoxy resin or a novolac epoxy resin.

The photo-conversion resin composition according to the present invention can effectively process the coating layer formation temperature at 100 to 250° C. by including a specific thermosetting agent, has excellent coating surface hardness, elastic recovery rate, and adhesion, and minimizes the amount of outgassing. In addition to being able to, by including a quantum dot into which a new ligand has been introduced, there is an effect of excellent dispersibility and optical properties.

The photo-conversion laminated substrate made of the photo-conversion resin composition and the image display device using the same have a simple structure and excellent reliability.

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

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

In the present invention, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise specified.

< Light conversion Resin composition>

The photoconversion resin composition of the present invention comprises a non-cadmium-based quantum dot containing a polyethylene glycol-based ligand, scattering particles, an alkali-soluble resin, a thermal curing agent and a solvent, and the thermal curing agent is a polyfunctional alicyclic epoxy resin or a novolac epoxy resin By including, the surface hardness, elastic recovery rate and adhesion of the coating film are excellent, and the amount of outgassing can be minimized, as well as the dispersibility and optical properties of the coating film are excellent by including quantum dots into which a new ligand is introduced.

Quantum dots

The photo-conversion resin composition according to the present invention is characterized in that it comprises a quantum dot containing a polyethylene glycol-based ligand.

Quantum dots included in the photoconversion resin composition of the present invention are nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When these nanoparticles have the characteristics of semiconductors, they are called quantum dots. These quantum dots have a characteristic of releasing energy corresponding to the energy band gap by themselves when they receive energy from the outside and reach an excited state. In short, since the photoconversion resin composition of the present invention includes such quantum dots, light conversion into green light and red light through an incident blue light source is possible.

The quantum dot is not particularly limited as long as it can emit light by stimulation by light, but it is more preferable that it is non-cadmium. For example, at least one selected from a group III-V semiconductor compound, a group IV-VI semiconductor compound, and a group IV element or a compound containing the same may be used.

The III-V group semiconductor compound is a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound 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 GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and one selected from the group consisting of a quaternary compound selected from the group consisting of mixtures thereof It can be more than that.

The IV-VI semiconductor compound is a binary compound 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 may be one or more selected from the group consisting of a quaternary compound selected from the group consisting of a mixture thereof.

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

The quantum dot has a homogeneous single structure; A dual structure such as a core-shell structure, a gradient structure, and the like; Or it may be a mixed structure of these. For example, in the dual structure of the core-shell, the material forming the core and the shell may be formed of the above-mentioned different semiconductor compounds.

According to an embodiment of the present invention, the core is a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound 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 GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and one selected from the group consisting of a quaternary compound selected from the group consisting of mixtures thereof It may include the above materials, but is not limited thereto. The shell may include at least one material selected from ZnSe, ZnS, and ZnTe.

According to an 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) process, but is not limited thereto. .

The quantum dots of the present invention include a polyethylene glycol-based ligand disposed on the surface, and 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 Chemical 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-chain alkyl group having 1 to 20 carbon atoms,

n is an integer from 2 to 100)

[Formula 1-1]

(In Formula 1-1,

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

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

* Means a bonded hand)

[Formula 1-2]

(In Formula 1-2,

R ₅ is an oxygen atom or a sulfur atom,

R ₆ is a direct linking group 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 a bond hand).

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

[Formula 2]

(In Chemical 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 (

), selected from the group consisting of a straight chain alkyl group having 1 to 20 carbon atoms and a branched chain alkyl group having 3 to 20 carbon atoms,

o is an integer of 0 to 5, p is an integer of 0 to 1, and q is an integer of 2 to 50).

As described above, when the polyethylene glycol-based ligand of the present invention contains the compound represented by Chemical Formula 2, there is an advantage in that dispersibility and optical properties are further improved.

In the present invention, the'alkyl group' may be a straight chain or branched chain unless otherwise specified, 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-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 are not limited thereto.

According to an embodiment of the present invention, the polyethylene glycol-based 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, 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), 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-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}- Oxy)-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-isobutoxy-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), 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-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, WAKO), 2-[2-(benzyloxy)ethoxy ]Acetic acid (2-[2-(Benzyloxy)ethoxy]acetic acid), (2-carboxymethoxy-ethoxy)-acetic acid ((2-Carboxymethoxy-ethoxy)-acetic acid, WAKO), (2-butoxy -Ethoxy)-acetic acid ((2-Butoxy-ethoxy)-acetic acid, WAKO) may be included.

As described above, the quantum dots of the present invention contain a polyethylene glycol-based ligand, so that a solvent such as propylene glycol monomethyl ether acetate used in the color filter mass production line is not used as a solvent with high volatility such as toluene, hexane, and chloroform. The dispersion characteristics of the quantum dots have a good effect.

The photoconversion resin composition of the present invention may further include quantum dots other than the non-cadmium-based quantum dots including the above-described 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. It may be included in an amount of 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the entire quantum dot not including a ligand. When the non-cadmium-based quantum dots including the polyethylene glycol-based ligand are included in the amount less than the above content range, the dispersion characteristics of the quantum dots may be deteriorated, and when it exceeds the above range, the curing properties of the coating film may be deteriorated.

According to an embodiment of the present invention, the quantum dots may include two or more types of quantum dots. When the quantum dots include two or more types of quantum dots, it is preferable because there is an advantage in that an image display device having more excellent color reproducibility can be provided.

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

In this case, the difference between the emission center wavelengths of the two or more types of quantum dots may be 70 nm or more. In this way, when two or more types of quantum dots having different emission center wavelengths are used, the color reproducibility can be further improved.

The non-cadmium-based quantum dots of the present invention may be included in an amount of 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 photo-conversion resin composition. When the quantum dots are included within 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 less than the above range, the photoconversion efficiency of green light and red light may be insufficient, and when the non-cadmium-based quantum dots are exceeded, the emission of blue light is relatively lowered, resulting in a problem in which color reproducibility is deteriorated. .

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 may preferably include a metal oxide having an average particle diameter of 50 to 1000 nm.

The metal oxides are 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, It may be an oxide containing one metal selected from the group consisting of Ce, Ta, In, and combinations thereof, but 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 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 also 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 1000 nm, and preferably those in the range of 100 to 500 nm may be used. At this time, if the particle size is too small, a sufficient scattering effect of the light emitted from the quantum dots cannot be expected. On the contrary, if the particle size is too large, it can be settled in the composition or a surface of the self-luminous layer of uniform quality cannot be obtained. Can be used.

The scattering particles may be included in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total solid content of the light conversion resin composition.

When the scattering particles are included within the above range, it is preferable that the effect of increasing the light emission intensity can be maximized. If the scattering particles are included within the above range, it may be somewhat difficult to secure the desired luminous intensity, and if the scattering particles exceed the above range, the transmittance of blue irradiation light may be significantly lowered, resulting in a problem in color reproducibility. It is desirable to use it appropriately.

Alkali-soluble resin

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

As the alkali-soluble resin, it may be selected from various polymers used in the applicable field of technology. The alkali-soluble resin is not particularly limited as long as it is a resin containing an acid value or a hydroxyl group, but from the viewpoint of shape or pattern step, adhesion to the substrate, and solvent resistance, epoxy (meth) acrylate-based resin, acrylic resin, carboxyl group-containing (alicyclic) Epoxy-based resins, novolac-based resins, and polyvinylphenol-based resins may be mentioned, but among them, epoxy (meth)acrylate-based resins or (alicyclic) epoxy-based resins may be more effective. A binder resin containing an (alicyclic) epoxy group is more preferable because it can improve reliability, such as chemical resistance and electrical properties, with little change over time.

In addition, the molecular weight of the alkali-soluble resin is preferably in the range of 3,000 to 40,000 by weight average molecular weight, 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 for an excellent balance of film-forming ability, reliability, and developability. 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 phenomena is excellent, and residue is generated. This is suppressed, and there is an advantage that the adhesion of the pattern is improved.

In the present invention, the "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 the total 100 parts by weight of the photoconversion resin composition.

When the alkali-soluble resin is included within the above range, it is preferable because it has sufficient solubility in a developer to facilitate pattern formation, and a film reduction in the pixel portion of the exposed portion is prevented during development, thereby improving the omission of non-pixel portions. When the alkali-soluble resin is included below the above range, the non-pixel portion may be slightly omitted, and when the alkali-soluble resin is included outside the above range, the solubility in the developer is slightly lowered, and thus pattern formation may be somewhat difficult.

Heat curing agent

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

The thermal curing agent not only has excellent surface hardness and adhesion of the coating film, but also has excellent elastic recovery rate in a high-temperature process, and minimizes the amount of outgas generated, thereby advantageously having an afterimage that may occur during panel operation.

The thermosetting agent of the present invention is characterized by comprising a polyfunctional alicyclic epoxy resin or a novolac epoxy resin, and thus has an advantage in securing stability over time than when using a silane-modified epoxy resin.

According to an embodiment of the present invention, the polyfunctional alicyclic epoxy resin may include 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 of 1 to 20).

[Formula 4]

In the present invention, the alkyl group may be linear or branched, 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 are not limited thereto.

Commercially available products of the polyfunctional alicyclic epoxy resin include Daicel Chemical Co., Ltd.'CEL-2021', alicyclic solid epoxy resin'EHPE-3150', epoxidized polybutadiene'PB3600', flexible alicyclic epoxy Compound "CEL-2081", lactone-modified epoxy resin "PCL-G", and the like can be used. In addition, Daicel Chemical Industry Co., Ltd.'s "Serocside 2000", "Epolide GT-3000", "GT-4000", etc. may be used, but the present invention is not limited thereto.

By using the multifunctional alicyclic epoxy resin, not only the surface hardness and adhesion of the coating film are excellent, but also the elastic recovery rate in the high-temperature process is excellent, and the amount of outgas is minimized, so that afterimages that may occur during panel operation There are benefits to it.

According to an 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).

As a commercial item of the novolac epoxy resin, Sumi Epoxy ESCN 195XL (manufactured by Sumitomo Chemical Industry Co., Ltd.) may be used, but is not limited thereto.

By using the novolac epoxy resin, not only the surface hardness and adhesion of the coating film are excellent, but also the elastic recovery rate in the high-temperature process is excellent, and the amount of outgas is minimized, which is beneficial for afterimages that may occur during panel operation. 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 solid content of the photo-conversion resin composition.

When the thermal curing agent satisfies the above range, the hardness of the coating film is improved, so that the surface hardness and adhesion of the coating film are excellent, and the elastic recovery rate in the high-temperature process is excellent, and the amount of outgas is minimized to occur during panel operation. There is a beneficial advantage for afterimages that are present. On the other hand, if the thermal curing agent is out of the above range, the surface hardness of the coating film may be lowered, adhesion may decrease, and crack may occur, and the elastic recovery rate in a high-temperature process may decrease, resulting in surface wrinkles. There is this. In addition, if the amount of outgas is increased, there is a risk of afterimages occurring during panel operation.

solvent

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

The solvent may contain at least one or more, and in particular, when a solvent having a boiling point of 100 to 240°C is contained 50% or more of the total solvent, the flow characteristics are excellent, so that coating stains and dry foreign matter do not occur. It is possible to provide a good light conversion laminated substrate without water.

If the solvent having a boiling point of less than 100°C is 50% or more of the total solvent, the drying speed is high and stains may occur on the surface of the coating film during the vacuum drying process, which may cause defects, whereas the solvent with a boiling point exceeding 240°C is 50% of the total solvent. If it is more than %, it may cause a problem of lengthening the tack-time during the vacuum drying process. Therefore, it is appropriate to use a solvent having a boiling point of 100 to 240°C for 50% or more 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 and amides, and 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-ethoxypropionate, propylene glycol diacetate, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl It may be one to two or more selected from the group consisting of ether, methoxybutyl acetate, ethylene glycol and γ-butyrolactone.

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, based on 100% by weight of the photoconversion resin composition. When the solvent is contained within the above range, the coating property may be improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an ink jet.

<Light conversion laminated substrate>

The photo-conversion laminated material according to the present invention includes a cured product of the photo-conversion resin composition. The photo-conversion laminated material includes a cured product of the photo-conversion resin composition, so that when forming a coating layer on the base material, it can be processed more effectively at a temperature of 100 to 250°C, and has luminance and long-term reliability compared to the existing complex structure. It 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 photo-conversion laminated substrate may be formed by applying the photo-conversion resin composition on the aforementioned substrate and exposing, developing, and thermosetting in a predetermined pattern.

<Image display device>

An image display device according to the present invention includes the above-described light conversion laminated substrate. Specifically, the image display device is a liquid crystal display (liquid crystal display; LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, and a display for a digital camera. A display device such as a device and a display device for car navigation. In particular, a color display device is suitable.

The image display device may further include a configuration known to a person skilled in the art, except that the photo-conversion laminate base material is provided, that is, the present invention applies the photo-conversion laminate base material of the present invention. It includes an image display device capable of.

Hereinafter, examples will be described in detail to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art. In addition, "%" and "parts" indicating the content hereinafter are based on weight unless otherwise noted.

Preparation of scattering particle dispersion

Preparation Example 1: Preparation of scattering particle dispersion S-1

_{TiO 2} (Huntsman TTO-55 (C)) 70.0 parts by weight as a scattering particle of 150 nm, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a dispersant, 26 parts by weight of propylene glycol methyl ether acetate as a solvent by a bead mill Mixing/dispersing for 12 hours to prepare a scattering particle dispersion S-1.

Synthesis Example 1: Synthesis of quantum dots

Synthesis Example 1-1: Synthesis of Green quantum dots (A-1)

Indium acetate (Indium acetate) 0.4mmol (0.058g), palmitic acid (palmitic acid) 0.6mmol (0.15g) and 1-octadecene (octadecene) 20mL was put into a reactor and heated to 120 ℃ under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating to 280 ℃, tris (trimethylsilyl) phosphine _{(TMS 3 P) 0.2mmol (58㎕} ) and trioctyl phosphine quickly injected a mixture of 1.0mL pin and allowed to react for 1 minute.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. 2 ml of the previously synthesized InP mixed solution was added, and then 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP/ZnSe core-shell.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. 2 ml of the previously synthesized InP/ZnSe core shell was added, and then 4.8 mmol of sulfur (S/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain InP/ZnSe/ZnS core-shell structured quantum dots, and dispersed in chloroform.

The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dots was 515 nm, 5 mL of the quantum dot solution was placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. Discard the supernatant separated through centrifugation, disperse the quantum dots by adding 2 mL of chloroform to the precipitate, and then add 0.5 g of O-(Succinyl)-O'-methylpolyethylene glycol 2'000 (Aldrich) and put it at 60℃ under nitrogen atmosphere. The reaction was carried out for one hour while heating with a furnace.

Then, 25 mL of n-hexane was added to the obtained reaction to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added and dispersed while heating at 80°C. The solid content was adjusted to 25% with 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)

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

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. After adding 2 mL of the previously synthesized InP mixed solution, 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP/ZnSe core-shell.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. 2 mL of the previously synthesized InP/ZnSe core-shell was added, followed by adding 4.8 mmol of sulfur (S/TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain InP/ZnSe/ZnS core-shell structured quantum dots, and then dispersed in chloroform.

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

Then, 25 mL of n-hexane was added to the reaction to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added and dispersed while heating at 80°C. The solid content was adjusted to 25% with 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)

Indium acetate (Indium acetate) 0.4mmol (0.058g), palmitic acid (palmitic acid) 0.6mmol (0.15g) and 1-octadecene (octadecene) 20mL was put into a reactor and heated to 120 ℃ under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating to 280 ℃, tris (trimethylsilyl) phosphine _{(TMS 3 P) 0.2mmol (58㎕} ) and trioctyl phosphine to promptly inject a mixture of 1.0mL pin and rapidly to room temperature, the reaction solution after 5 minutes reaction Cooled down.

Zinc acetate 2.4mmoL (0.448g), oleic acid 4.8mmol, and trioctylamine 20mL were put into 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 heated to 280°C. After adding 2 mL of the previously synthesized InP mixed solution, 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, the final mixture was reacted for 2 hours and then lowered to room temperature to form an InP/ZnSe core-shell.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. 2 mL of the previously synthesized InP/ZnSe core-shell was added, followed by adding 4.8 mmol of sulfur (S/TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain InP/ZnSe/ZnS core-shell structured quantum dots, and 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 added to precipitate. Discard the supernatant separated by centrifugation, disperse the quantum dots by adding 2 mL of chloroform to the precipitate, and then add 0.65 g of 2-[2-(2-Methoxyethoxy)ethoxy]acetic acid (from WAKO) to 60℃ under a nitrogen atmosphere. The reaction was carried out for an hour while heating with a furnace.

Then, 25 mL of n-hexane was added to the reaction to precipitate the quantum dots, followed by centrifugation to discard the supernatant and to separate the precipitate, and then 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added and dispersed while heating to 80°C. . At this time, the solid content was adjusted to 25% with PGMEA. The maximum emission wavelength of the finally obtained quantum dot was 628 nm.

Synthesis Example 1-4: Red quantum dot synthesis (A-4)

Indium acetate (Indium acetate) 0.4mmol (0.058g), palmitic acid (palmitic acid) 0.6mmol (0.15g) and 1-octadecene (octadecene) 20mL was put into a reactor and heated to 120 ℃ under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating to 280 ℃, tris (trimethylsilyl) phosphine as _{(TMS 3 P) 0.2mmol (58㎕} ) and trioctyl phosphine quickly injected a mixture of 1.0mL and quickly to room temperature, the reaction solution after the reaction 4.5 minutes Cooled down.

Zinc acetate 2.4mmoL (0.448g), oleic acid 4.8mmol, and trioctylamine 20mL were put into 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 heated to 280°C. After adding 2 mL of the previously synthesized InP mixed solution, 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, the final mixture was reacted for 2 hours and then lowered to room temperature to form an InP/ZnSe core-shell.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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 heated to 280°C. 2 mL of the previously synthesized InP/ZnSe core-shell was added, and then 4.8 mmol of sulfur (S/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain InP/ZnSe/ZnS core-shell structured quantum dots, and then dispersed in chloroform.

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

Then, 25 mL of n-hexane was added to the reaction to precipitate the quantum dots, followed by centrifugation to discard the supernatant and to separate the precipitate, and then 4 mL of propylene glycol monomethyl ether acetate (PGMEA) was added and dispersed while heating to 80°C. . At this time, the solid content was adjusted to 25% with 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 introduction 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, PGMEA) were added and mixed with stirring to prepare a dropping lot of monomers, and 6 parts by weight of n-dodecanethiol , 24 parts by weight of PGMEA were added and mixed with stirring to prepare a chain transfer agent dropping lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Next, dropping of the monomer and the chain transfer agent was started from the dropping lot. Dropping proceeds for 2 hours while maintaining 90°C, and after 1 hour the temperature is raised to 110°C and maintained for 3 hours, and then the gas introduction tube is introduced, and the bubble of the mixed gas of oxygen/nitrogen = 5/95 (v/v) Started the ring. Then, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were added into the flask, and at 110° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH/g was obtained.

Examples 1 to 12 and Comparative Examples 1 to 14: Preparation of photoconversion resin composition

A photoconversion resin composition according to Examples and Comparative Examples was prepared using the components and contents (% by weight) of Table 1 below.

Quantum dots Scattering particles Alkali-soluble resin Heat curing 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 14 8.0 - 0.7 - - - 0.7 27.2 - - - 63.4 A-1: Quantum dots of Synthesis Example 1-1
A-2: Quantum dots of Synthesis Example 1-2
A-3: Quantum dots of Synthesis Example 1-3
A-4: Quantum dots of Synthesis Example 1-4
A-5: InP/ZnS oleylamine ligand toluene solution (emission center wavelength 560nm, half width 80nm, Aldrich)
A-6: InP/ZnS oleylamine ligand toluene solution (emission 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 (manufactured by Daicel Chemical Industry Co., Ltd.)
D-2: Sumi Epoxy ESCN 195XL (manufactured by Sumitomo Chemical Industries, Ltd.)
D-3: Composeran E-101 (manufactured by Arakawa Chemical Industries, Ltd.)
E: Propylene glycol monomethyl ether acetate
* In the case of the comparative example, the toluene solvent contained in the ligand was removed under reduced pressure, and then propylene glycol monomethyl ether acetate was supplemented by the amount of the removed toluene solvent.

Experimental example

The photo-conversion coating layer was prepared as follows using the photo-conversion resin composition prepared in the above Examples and Comparative Examples, and at this time, the coating luminance, color reproducibility, surface hardness, elastic recovery rate, adhesion, outgas generation amount and rate of change over time Was measured in the following manner, and the results are shown in Table 2 below.

(One) Light conversion Coating layer manufacturing

A coating film was prepared using the photoconversion resin composition prepared in Examples and Comparative Examples. That is, after applying each of the photo-conversion resin compositions on a 5cm × 5cm glass substrate by spin coating, placing them on a heating plate and holding them at a temperature of 100°C for 10 minutes to form a thin film, and then in a heating oven at 180°C for 30 minutes. It was heated to prepare a light conversion coating layer. The thickness of the photo-conversion resin film prepared above was manufactured to a thickness of 8.0 μm according to the content of the quantum dots.

(2) luminance

After placing the coating film prepared in (1) above the blue light source (XLamp XR-E LED, Royal blue 450, Cree), and using a luminance meter (CAS140CT Spectrometer, Instrument Systems, Inc.), measured brightness when irradiated with blue light. Was measured, and the evaluation results are shown in Table 2 below.

(3) Color reproducibility

The coating film prepared in (1) above is placed on a blue light source (XLamp XR-E LED, Royal blue 450, Cree), and a color filter substrate (UN65, Samsung Electronics TV Color) with red, green, and blue patterns thereon. filter), and then using a colorimeter (OSP-200, Olympus) to measure the color coordinates of red, green, and blue, and calculate the area ratio to the NTSC color gamut for the color reproduction area expressed at this time. The results are shown in Table 2 below.

(4) Surface hardness of the coating film

The curing degree of the coating film prepared in (1) was measured at a high temperature of 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 surface hardness of the coating film was evaluated based on the following criteria.

<Evaluation criteria>

○: surface hardness 50 or more

△: surface hardness of 30 or more and less than 50

×: surface hardness less than 30

(5) Elastic recovery rate

The elastic recovery rate of the coating film prepared in (1) was measured using a Fisher hardness tester (fisherscope HM-2000, Fisher Co.), and a force was applied to the coating film prepared in (1) up to 50 mN, and the results are shown in Table 2 below. Indicated.

<Evaluation Criteria>

○: Excellent, elastic recovery rate of 60 or more

△: insufficient, elastic recovery rate 30 or more and less than 60

×: deterioration, elastic recovery rate less than 30

(6) adhesion

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

<Evaluation Criteria>

○: Maintain more than 90 patterns

△: 60 to 89 patterns are maintained

×: 9 to 59 patterns are maintained

(7) Outgas ( outgas ) Generation

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

At this time, the amount of outgas generated was evaluated based on the following criteria, and the obtained results 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), the initial viscosity of the day on which the prepared photo-conversion resin composition was prepared and the viscosity after storage at room temperature for 1 month were measured to determine whether the change over time. The measurement was made at 25°C under conditions of a rotation speed of 50 rpm using a viscometer (TV-35 viscometer manufactured by Togi Sangyo Co., Ltd.).

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

<Evaluation Criteria>

The rate of change in viscosity 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] = (Elapsed viscosity/Initial viscosity) Х100

(9) Haze

For the light conversion resin composition in which the scattering particles were not added in the Examples and Comparative Examples, haze was measured using a haze meter (HZ-1, manufactured by Suga), and the obtained results are shown in Table 2 below. I got it.

<Evaluation criteria>

A haze value of 8.0 or less should be a good level.

Luminance
(nit) Color reproducibility
(% of NTSC) Film hardness Shout
Recovery rate Adhesion Outgas
(%) Haze Rate of 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 14 3915 98.4 × × × 190 1.2 100.3

Referring to Table 2, in the case of Examples 1 to 12 that satisfy all the configurations presented in the present invention, the luminance and color reproducibility are compared to the case of Comparative Examples 1 to 14 that do not satisfy any of the configurations presented in the present invention. It was confirmed that, as well as optical properties such as haze, film hardness, elastic recovery rate, adhesion, outgassing prevention, and aging change rate, more excellent effects were shown.

Specifically, in the case of Comparative Examples 1 to 10 that do not satisfy the configuration of the quantum dots presented in the present invention, the quantum efficiency of the quantum dots is lowered due to poor liquid dispersibility, thereby reducing luminance and color reproducibility, and increasing the haze. It was confirmed that the properties were poor, and in the case of Comparative Examples 5 to 8 and Comparative Example 11 including a silane-modified epoxy resin as a heat curing agent, it was confirmed that the rate of change over time was not good. In particular, in the case of Comparative Example 14, which did not contain any thermal curing agent, it was confirmed that the coating film hardness, elastic recovery rate, and adhesion were all poor.

Claims (15)

Including two or more kinds of non-cadmium-based quantum dots including a polyethylene glycol-based ligand, scattering particles, alkali-soluble resin, a thermosetting agent and a solvent,
The thermosetting agent is a photoconversion resin composition comprising a polyfunctional alicyclic epoxy resin or a novolac epoxy resin. The method of claim 1,
The polyethylene glycol-based ligand is a photoconversion resin composition comprising a compound represented by the following formula (1):
[Formula 1]

(In Chemical 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-chain alkyl group having 1 to 20 carbon atoms,
n is an integer from 2 to 100)
[Formula 1-1]

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

(In Formula 1-2,
R ₅ is an oxygen atom or a sulfur atom,
R ₆ is a direct linking group 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 a bond hand). delete The method of claim 2,
The compound of Formula 1 is a photoconversion resin composition comprising a compound represented by Formula 2 below:
[Formula 2]

(In Chemical Formula 2,
R ₂ is mercapto (

), carboxylic acid (

), dithioacetic acid (

), phosphoric acid (

), amine (

), selected from the group consisting of a straight chain alkyl group having 1 to 20 carbon atoms and a branched chain alkyl group having 3 to 20 carbon atoms,
o is an integer of 0 to 5, p is an integer of 0 to 1, and q is an integer of 2 to 50). The method of claim 1,
The polyfunctional alicyclic epoxy resin is a photoconversion resin composition, characterized in that it comprises 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 of 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 thermal curing agent is a photoconversion resin composition, characterized in that contained in an amount of 0.1 to 40% by weight, based on 100% by weight of the total solid content of the photoconversion resin composition comprising the same. The method of claim 1,
The quantum dot is
A binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound 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 GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and one selected from the group consisting of a quaternary compound selected from the group consisting of mixtures thereof A core containing the above materials; And
A photoconversion resin composition comprising: a shell comprising at least one material selected from ZnSe, ZnS, and ZnTe. The method of claim 1,
The quantum dots include at least one selected from the group consisting of InP/ZnS, InP/ZnSe, InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS and InP/MnSe/ZnS. Photo-conversion resin composition. The method of claim 1,
The quantum dot is a green quantum dot having an emission center wavelength range of 510nm to 540nm; And a red quantum dot having a light emission center wavelength range of 610 nm to 630 nm. The method of claim 10,
The quantum dot is a photo-conversion resin composition, characterized in that the light emission center wavelength comprises two or more kinds of quantum dots having a difference of 70 nm or more from each other. The method of claim 1,
The polyethylene glycol-based ligand is 2-(2-methoxyethoxy)acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, succinate 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, {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 Oxy]-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] ester, 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-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, (2-butoxy-ethoxy)-acetic acid, carboxy-EG6-undecanthiol, and (2-carboxymethoxy-ethoxy)-acetic acid A photoconversion resin composition comprising at least one selected from. 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 laminate comprising a cured product of the photoconversion resin composition according to any one of claims 1, 2, and 4 to 13. An image display device comprising the light conversion laminated substrate according to claim 14.