KR102582006B1 - Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The photosensitive resin composition of embodiments of the present invention includes quantum dot particles including a ligand having a thiol group and a cyclic ether group. By including a cyclic ether group, the dispersibility of the composition in a solvent can be improved. The composition can be used to form a photocurable pattern with excellent optical properties and an image display device including the same.

Description

Photosensitive resin composition, photocurable pattern formed therefrom, and image display device comprising the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOCURABLE PATTERN FORMED FROM THE SAME AND IMAGE DISPLAY COMPRISING THE PATTERN}

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same. More specifically, it relates to a photosensitive resin composition containing quantum dot particles, a photocurable pattern formed therefrom, and an image display device containing the same.

A color filter is a thin film-type optical component that extracts three colors, red, green, and blue, from white light and functions in tiny pixel units. The size of one pixel is about tens to hundreds of micrometers. The color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a plurality of colors (typically red (R), green (G), and It has a structure in which pixel units in which the three primary colors (blue (B)) are arranged in a certain order are stacked one after another. In general, color filters can be manufactured by coating three or more colors on a transparent substrate using dyeing, electrodeposition, printing, or pigment dispersion methods. Recently, pigment dispersion methods using pigment-dispersed photosensitive resins are mainly used. there is.

According to the pigment dispersion method, which is one of the methods of implementing a color filter, first, a photosensitive resin composition containing a colorant, alkali-soluble resin, photopolymerization monomer, photopolymerization initiator, epoxy resin, solvent, and other additives is deposited on a transparent substrate provided with a black matrix. Coat on the substrate. Afterwards, a colored thin film can be formed by repeating a series of processes of exposing the pattern of the shape to be formed, removing the non-exposed area with a solvent and heat curing.

However, color reproduction is achieved by light emitted from a light source passing through a color filter, and in this process, part of the light is absorbed by the color filter, which may reduce light efficiency. Additionally, perfect color reproducibility may not be secured due to the characteristics of the pigment as a color filter.

Korean Patent Publication No. 10-2012-112188 discloses an example of a red coloring composition for a color filter and a color filter.

Korean Patent Publication No. 10-2012-112188

One object of the present invention is to provide a photosensitive resin composition having excellent dispersibility and optical properties.

One object of the present invention is to provide a photocurable pattern formed from the photosensitive resin composition and an image display device including the same.

1. A photosensitive resin composition comprising quantum dot particles containing a ligand having a thiol group and a cyclic ether group.

2. The photosensitive resin composition of 1 above, wherein the cyclic ether group is a tetrahydrofuranyl group.

3. The photosensitive resin composition of 1 above, wherein the quantum dot particles include a ligand represented by the following formula (1):

[Formula 1]

(In Formula 1 above,

L is a divalent hydrocarbon group that may contain a carbonyl group,

The divalent hydrocarbon group is a substituted or unsubstituted alkylene group having 1 to 13 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 13 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms. It is selected from the group consisting of a cycloalkylene group having 3 to 13 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 13 carbon atoms, and a substituted or unsubstituted cycloalkynylene group having 3 to 13 carbon atoms,

n is an integer from 0 to 10).

4. The photosensitive resin composition of 1 above, wherein the quantum dot particles include at least one selected from the group consisting of ligands represented by the following Formulas 2-1 to 2-19.

5. The method of 1 above, wherein the quantum dot particles are photosensitive, comprising at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, or a compound containing the same. Resin composition.

6. The photosensitive resin composition of 1 above, wherein the quantum dot particles include a core and a shell covering the core.

7. The photosensitive resin composition of 6 above, wherein the core contains indium and phosphorus, and the shell contains zinc, selenium, and sulfur.

8. The method of 6 above, wherein the shell includes a first shell layer covering the core and a second shell layer covering the first shell layer, the core includes InP or InZnP, and the first shell layer includes ZnSe or ZnSeS. and wherein the second shell layer includes ZnS.

9. The photosensitive resin composition of 1 above, wherein the photosensitive resin composition further includes at least one of a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.

10. A photocurable pattern formed from a photosensitive resin composition containing quantum dot particles containing a ligand having a thiol group and a cyclic ether group.

11. An image display device comprising a photocurable pattern formed from a photosensitive resin composition containing quantum dot particles containing a ligand having a thiol group and a cyclic ether group.

The photosensitive resin composition according to embodiments of the present invention can provide excellent optical properties by including quantum dot particles.

In addition, the photosensitive resin composition according to exemplary embodiments of the present invention has quantum dot particles containing a ligand having a thiol group and a cyclic ether group, and thus can achieve excellent dispersibility and solubility in polar solvents.

In addition, a photocurable pattern with excellent light efficiency and durability and an image display device including the same can be formed using the photosensitive resin composition according to exemplary embodiments of the present invention.

According to embodiments of the present invention, a photosensitive resin composition including quantum dot particles including a ligand having a thiol group and a cyclic ether group is provided. As the quantum dot particles contain a ligand having a thiol group and a cyclic ether group, their solubility in a solvent and optical properties may be excellent at the same time.

In addition, a photocurable pattern manufactured from the photosensitive resin composition and having improved optical properties and light durability, and an image display device including the photocurable pattern are provided.

Hereinafter, photosensitive resin compositions according to embodiments of the present invention will be described in detail. If there are isomers of the compound or resin represented by the chemical formula used in this application, the compound or resin represented by the chemical formula means the representative chemical formula including the isomers.

Below, embodiments of the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition according to embodiments of the present invention may include quantum dot particles including a ligand having a thiol group and a cyclic ether group, and further includes a binder resin, a solvent, a polymerizable compound, a polymerization initiator, and other additives. can do.

quantum dot particles

The photosensitive resin composition according to exemplary embodiments may include quantum dot particles including a ligand having a thiol group and a cyclic ether group. For example, the ligand may include quantum dot particles disposed on the surface.

Quantum dots are nano-sized semiconductor materials. Specifically, atoms form molecules, and molecules form a collection of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots.

When the quantum dot particle receives energy from the outside and reaches an excited state, it emits energy (for example, light) according to the energy band gap of the quantum dot. Specifically, quantum dot particles are capable of photoluminescence, which emits light by light irradiation, or electroluminescence, which emits light by applying electric current, and are used as light-emitting materials in various fields such as display devices, energy devices, or bioluminescent devices. It is applicable as.

For example, quantum dot particles can be used in LCD (Liquid Crystal Diodes)-based displays using photoluminescent devices or QLED (Quantum dot Light Emitting Diodes)-based displays using electroluminescent devices.

Since the photosensitive resin composition according to exemplary embodiments includes such quantum dot particles, for example, a color filter manufactured from the photosensitive resin composition may emit light when irradiated with light.

Quantum dot particles can control the energy band gap of quantum dots by controlling the size and/or composition of the nanocrystals. For example, as the size of a quantum dot particle decreases, it can have a wider energy band gap and the emission wavelength can decrease. Therefore, by adjusting the particle size and/or composition of the quantum dot particles, quantum dot particles that emit light of a desired wavelength can be implemented.

For example, the quantum dot particles may be blue quantum dots that emit blue light, green quantum dots that emit green light, or red quantum dots that emit red light. In the case of the green quantum dots or red quantum dots, the irradiated blue light source can be light converted into green light or red light.

Additionally, in a general image display device that includes a color filter, a portion of the light may be absorbed by the color filter in the process of realizing color by transmitting white light through the color filter. Accordingly, light efficiency may decrease in the process of transmitting through the color filter.

However, when a color filter made of a photosensitive resin composition according to exemplary embodiments is included, the color filter self-lumines by light from a light source, thereby achieving greater light efficiency.

According to exemplary embodiments, the quantum dot particle is a material that can emit light when stimulated by light, for example, a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, or It may include compounds containing this, and mixtures thereof. These may be used alone or in combination of two or more.

The II-VI group compounds include binary compounds selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS and mixtures thereof; a ternary compound selected from CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and a tetraelement compound selected from CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

The III-V group compounds include binary compounds selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound selected from GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and a tetraelement compound selected from GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

The Group IV-VI compounds include binary compounds selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and a quaternary element compound selected from SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

The Group IV element or a compound containing it is a compound of an element selected from Si, Ge, and mixtures thereof; and a binary compound selected from SiC, SiGe, and mixtures thereof.

According to exemplary embodiments, the quantum dot particles may have a homogeneous single structure, a core-shell structure, a gradient structure, or a mixture thereof.

In some embodiments, the quantum dot particles may have a core-shell structure consisting of a core and a shell covering the core. The core may be a part where light emission actually occurs, and the shell may serve to prevent oxidation of the core and reduce the trap energy level on the surface to improve the stability and light efficiency of the quantum dot particles.

The materials that make up each core and shell may be made of the different compounds described above. For example, the core may be GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InNP, InZnP, InNAs, InNSb, InPAs, InPSb GaInPAs, GaInPSb, InAlNP, InAlNAs, It may include one or more materials selected from the group consisting of InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The shell may include one or more materials selected from the group consisting of ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, ZnSe, ZnS, ZnSeS, and mixtures thereof. Preferably, the core may include In and P, and the shell may include Zn, Se and/or S.

In some embodiments, the shell may have a multi-layered shell structure including one or more shell layers. For example, the quantum dot particle may include a core, a first shell layer covering the core, and a second shell layer covering the first shell layer.

In some embodiments, adjacent core and shell layers in the multi-layer shell structure may have different compositions. For example, the core may include InP, and/or InZnP, the first shell layer may include ZnSe and/or ZnSeS, and the second shell layer may include ZnS.

In some embodiments, the quantum dot particles may be non-cadmium-based quantum dots that substantially do not contain cadmium (Cd). Accordingly, environmental or health hazards caused by cadmium can be prevented.

The quantum dot particles may have a ligand having a thiol group and a cyclic ether group disposed on the surface. For example, the ligand may be a substituted or unsubstituted aliphatic hydrocarbon having a thiol group at one end and a cyclic ether group at the other end.

The thiol group of the ligand may be chemically bonded to the surface of the quantum dot particle. For example, the thiol group of the ligand may form a coordination bond with Zn included in the shell of the quantum dot particle.

In general, the ligand used in quantum dots consists of an aliphatic group with a high carbon content, so it is mainly soluble only in non-polar solvents, and its dispersibility in polar organic solvents and water is not sufficiently realized. Accordingly, for example, compatibility in image display devices was poor and sufficient light efficiency was not provided.

However, the photosensitive resin composition according to exemplary embodiments includes a highly polar cyclic ether group at the end of the ligand, so that the quantum dot particles may be polar, and thus the dispersibility in polar solvents may be improved. .

In some embodiments, the cyclic ether group may be tetrahydrofuranyl. Since the tetrahydrofuranyl group has high polarity, it can improve dispersibility in polar solvents compared to a ligand having an alkyl group or linear ether group at the terminal.

In addition, the quantum dot particles may have increased intermolecular interactions as the highly polar tetrahydrofuranyl group is disposed on the surface, and thus may have excellent curing properties. For example, a photocurable pattern formed from a photosensitive resin composition containing the quantum dot particles may have excellent durability.

Additionally, the ligand generally used in quantum dots has an overall linear structure, so oxygen or moisture can easily enter the core of the quantum dot particle. In this case, the quantum dot particles may be oxidized by oxygen or moisture, which may reduce the light efficiency of the photocuring pattern.

However, since the cyclic ether group or tetrahydrofuranyl group according to exemplary embodiments has a bulky structure, the permeability of oxygen or moisture may be reduced due to steric hindrance of the ligand. . For example, the ligand can function as a kind of protective layer that prevents oxidation of quantum dot particles by oxygen or moisture.

Therefore, the photosensitive resin composition according to exemplary embodiments can achieve excellent light efficiency by including a ligand having a cyclic ether group or a tetrahydrofuranyl group.

According to exemplary embodiments, the quantum dot particle may include a ligand represented by Formula 1 below.

[Formula 1]

In Formula 1, L may be a divalent hydrocarbon group that may include a carbonyl group.

The divalent hydrocarbon group is a substituted or unsubstituted alkylene group having 1 to 13 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 13 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms. It may be a cycloalkylene group with 3 to 13 carbon atoms, a substituted or unsubstituted cycloalkenylene group with 3 to 13 carbon atoms, or a substituted or unsubstituted cycloalkynylene group with 3 to 13 carbon atoms. In some embodiments, the alkylene group, alkenylene group, alkynylene group, cycloalkylene group, cycloalkenylene group, and cycloalkynylene group may each independently include one or more carbonyl groups in the carbon chain.

The term “substituted” means substituted with at least one selected from the group consisting of a halogen atom, hetero atom, hydroxy group, carboxyl group, amino group, cyano group, nitro group, and thiol group.

In Formula 1, n may be an integer from 0 to 10.

As shown in Formula 1, the ligand has a tetrahydrofuranyl group, a cyclic ether group, at the terminal, so it can stably maintain solubility and dispersibility in polar organic solvents and improve the optical properties and durability of the photocurable pattern. You can do it.

In some embodiments, the quantum dot particles may include at least one selected from the group consisting of ligands represented by the following formulas 2-1 to 2-19.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

In some embodiments, the content of the ligand may be about 30 to 200% by weight of the total weight of the quantum dot particles (eg, core and shell) excluding the ligand. If the content of the ligand is less than about 30% by weight, the dispersibility of the quantum dot particles in the solvent may not be sufficiently provided. If the content of the ligand exceeds about 200% by weight, the degree of curing of the photocurable pattern may decrease due to the ligand. Preferably, the ligand may be included in about 50 to 150% by weight of the total weight of the quantum dot particles.

According to exemplary embodiments, the average particle diameter of the quantum dot particles may be about 5 to 12 nm. In some embodiments, when the quantum dot particles have a core-shell structure, the average particle diameter of the core may be about 2.5 to 5 nm, and the thickness of the shell may be about 2.5 to 7 nm. When the average particle diameter and thickness are within the above range, the dispersibility of the quantum dot particles is improved, and the desired color can be realized by light irradiation.

In some embodiments, the content of the quantum dot particles may be about 1 to 30% by weight of the total solid weight of the photosensitive resin composition. If the content of the quantum dot particles is less than 1% by weight, the luminous efficiency by the quantum dot particles may decrease. When the content of the quantum dot particles is more than 30% by weight, it may be difficult to form a photocuring pattern due to the relatively insufficient content of other compositions. Preferably, the quantum dot particles may be included in about 3 to 20% by weight of the total solid weight of the photosensitive resin composition.

In some embodiments, the quantum dot particles may be synthesized by a wet chemical process, metal organic chemical vapor deposition (MOCVD), or molecular beam epitaxy (MBE). You can. The wet chemical process is a method of growing particles by adding precursor materials to an organic solvent. When a crystal grows, the organic solvent is coordinated to the surface of the quantum dot crystal, acts as a dispersant, and regulates the growth of the crystal. Accordingly, the growth of crystals can be controlled through an easier and cheaper process than vapor deposition methods such as an organometallic chemical vapor deposition process or a molecular beam epitaxy process.

binder resin

The binder resin may include a thermosetting resin or an alkali-soluble resin. The binder resin may be a component that provides solubility to an alkaline developer used in the development process when forming a pattern.

In some embodiments, the binder resin may include an acrylic resin, a cardo-based resin, or an epoxy resin. These may be used alone or in combination of two or more. Preferably, it may be an acrylic resin and/or a cardo-based resin.

For example, acrylic resins include polybenzyl methacrylate, meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2- It may include hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc.

For example, the epoxy resin may include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.

For example, cardo-based resins include fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic acid dianhydride, Anhydride compounds such as rylene tetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

The binder resin has reactivity to light or heat and can improve the dispersibility of quantum dot particles. Additionally, it can act as a binder resin for quantum dots and can be used as a support for photocuring patterns.

In some embodiments, the binder resin may be included in about 5 to 80% by weight of the total solid weight of the photosensitive resin composition. Within the above range, the solubility in the developer is sufficient so that pattern formation can be facilitated. Additionally, film reduction in the pixel portion of the exposed area can be prevented during development, thereby reducing omission of non-pixel portions. Preferably, it may be included in about 10 to 70% by weight of the total solid weight of the photosensitive resin composition.

menstruum

In some embodiments, the photosensitive resin composition may include a solvent. The solvent may include an organic solvent that sufficiently dissolves the quantum dot particles and binder resin described above and does not cause precipitation of components of the composition.

When the photosensitive resin composition includes quantum dot particles, it is difficult to use polar organic solvents such as propylene glycol monomethyl ether acetate and ethylenediclycolmethylethyl ether, which are generally used in the photosensitive resin composition.

However, as described above, the photosensitive resin composition according to exemplary embodiments allows the use of polar organic solvents and improves light efficiency as a ligand having a cyclic ether group is disposed on the surface of the quantum dot.

Specific examples of the solvent include ethylene glycol monoalkyl ethers; Diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetate; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; Butyldiol monoalkyl ethers; Butanediol monoalkyl ether acetate; Butanediol monoalkyl ether propionates; Dipropylene glycol dimethyl ether, dipropylene glycol dialkyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Alcohols such as methanol and ethanol; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic esters such as γ-butyrolactone, etc. can be mentioned. These may be used alone or in combination of two or more types. Preferably, the solvent may include propylene glycol monomethyl ether (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA).

The solvent may be included in the remaining amount excluding the components of the composition described above, for example, the remaining amount excluding the quantum dot particles, or the remaining amount excluding the quantum dot particles, binder resin, and other additive components.

In some embodiments, the solvent may be included in about 40 to 95% by weight, preferably about 45 to 85% by weight, of the total weight of the photosensitive resin composition. Within the above range, the applicability and drying properties of the composition can be improved, and the coating can be easily formed through an application method using a spin coater, slit and spin coater, slit coater, die coater, curtain flow coater, inkjet, etc. .

polymerizable compound

In some embodiments, the photosensitive resin composition may include a polymerizable compound. A polymerizable compound is a compound that can be polymerized or crosslinked by the action of a polymerization initiator, which will be described later, and can increase the crosslinking density during the manufacturing process and strengthen the mechanical properties of the photocured pattern.

The polymerizable compound may be used without particular limitation as long as it is used in the art, and may include, for example, a monofunctional monomer, a difunctional monomer, or a trifunctional or more polyfunctional monomer. These may be used alone or in combination of two or more.

The monofunctional monomer may be nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. .

Bifunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and bisphenol A. It may be (acryloyloxyethyl) ether, 3-methylpentanediol di(meth)acrylate, etc.

The multifunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth) ) Acrylate, dipentaerythritol hexa(meth)acrylate, etc.

In some embodiments, the content of the polymerizable compound may be about 30 to 85% by weight, preferably about 40 to 80% by weight, based on the total solid weight of the photosensitive resin composition. When the polymerizable compound is included in the above content range, the durability of the photocurable film can be improved, and the resolution of the composition during the development process can be improved.

polymerization initiator

In some embodiments, the photosensitive resin composition may include a polymerization initiator.

The polymerization initiator may be used without particular limitation as long as it can induce a crosslinking reaction or polymerization reaction of the polymerizable compound through, for example, an exposure process. For example, the polymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a benzoin-based compound, a triazine-based compound, a biimidazole-based compound, a thioxanthone-based compound, an oxime ester-based compound, etc., preferably An oxime ester-based compound may be used.

The oxime ester compounds include o-ethoxycarbonyl-α-oxymino-1-phenylpropan-1-one, 1,2-octadione-1-(4-phenylthio)phenyl-2-(o-benzoyl) oxime), ethanone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), etc., and a commercially available product is CGI-124 (Ciba). Geiger), CGI-224 (Shiba Geige), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeka), NCI-831 (Adeka), etc. there is. These may be used alone or in combination of two or more.

In some embodiments, a polymerization initiation aid may be additionally used to improve the sensitivity of the photosensitive resin composition. Examples of the polymerization initiation aid include amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

The content of the polymerization initiator is not particularly limited, but for example, may be included in about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight, based on the total weight of solids of the photosensitive resin composition. Within the above range, the efficiency and resolution of the exposure process can be improved without impairing the durability of the photosensitive resin composition.

Other additives

The photosensitive resin composition according to exemplary embodiments may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet ray absorbers, aggregation inhibitors, and chain transfer agents, as needed.

Additionally, quantum dot particles according to exemplary embodiments may include other organic or inorganic ligands on their surfaces to the extent that they do not impair the characteristics of the ligand having a thiol group and a cyclic ether group. The organic or inorganic ligand forms a coordination bond on the surface of the quantum dot particles and can improve the dispersibility and luminescence properties of the quantum dot particles.

For example, the organic ligands include trioctylphosphine, trioctylphosphine oxide, oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid, and tetradecylphosph. It may include phonetic acid, octylphosphinic acid, etc. The inorganic ligand may include inorganic substances such as halogen, metal halide, chalcogen, metal chalcogenide, metal hydroxide, and SCN-. These may be used alone or in combination of two or more.

<Photocuring pattern and image display device>

The present invention provides a photocurable pattern manufactured from a photosensitive resin composition according to exemplary embodiments and an image display device including the photocurable pattern. For example, the photocurable pattern can be used as a color filter in an image display device, as will be described later.

In forming the photocurable pattern, a photosensitive resin composition according to exemplary embodiments may be applied on a substrate to form a photosensitive film. Application methods include, for example, inkjet printing, spin coating, flexible coating, roll coating, slit and spin coating, or slit coating. After forming the photosensitive film, a pre-baking process may be performed to remove volatile components such as solvents.

After this, an exposure process can be performed to form a photocurable film. In order to form a desired pattern, ultraviolet rays may be irradiated through an exposure mask of a predetermined type. Curing may occur in the area irradiated with the ultraviolet rays. As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc. can be used.

After the exposure process, a development process may be performed to form a photocuring pattern. For example, a photocurable pattern can be formed by removing non-exposed areas using an alkaline developer. Alternatively, a photocurable pattern can be formed by removing the exposed area using an alkaline developer. The development process includes liquid addition method, dipping method, spray method, etc. After the exposure process or the development process, a post baking process may be further performed.

According to exemplary embodiments, the photocurable pattern may be used in a color filter. The color filter including the photocurable pattern can be applied to various image display devices such as electroluminescence display devices, plasma displays, and field emission displays as well as conventional liquid crystal displays.

The color filter may include a substrate and a photocurable pattern layer formed on top of the substrate. For example, the substrate may be the color filter itself, or may be a portion where the color filter is located in a display device, etc. The substrate may be glass, silicon, silicon oxide, or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

When the color filter is applied to an image display device, better light efficiency can be achieved because the quantum dot particles emit light from a light source. In addition, since colored light is emitted, color reproducibility can be excellent, and since light is emitted in all directions by the quantum dot particles, the viewing angle can also be improved.

In some embodiments, the color filter may include a transparent pattern layer, a green pattern layer that converts incident blue light into green light, or a red pattern layer that converts incident blue light into red light. The green pattern layer may include green quantum dots that emit green light when irradiated with blue light, and the red pattern layer may include red quantum dots that emit red light when irradiated with blue light.

In some embodiments, the image display device may include a color filter including a transparent pattern layer, a green pattern layer, and a red pattern layer. In this case, a light source that emits blue light can be used as the light source of the image display device.

As described above, the photosensitive resin composition can prevent oxidation of quantum dot particles by containing a ligand having a cyclic ether group, and thus a photocurable pattern with excellent optical properties can be provided. Accordingly, the loss of light irradiated to the color filter including the photocuring pattern can be minimized and converted more efficiently, thereby realizing excellent light efficiency.

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid understanding of the present invention, but these are only illustrative of the present invention and do not limit the scope of the appended claims, and do not limit the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope, and it is natural that such changes and modifications fall within the scope of the appended patent claims.

Synthesis example: quantum dot particles

Synthesis Example 1: A-1

A solution in which quantum dot particles of the InP/ZnSe/ZnS core-shell structure are dispersed (quantum dot solid content 30%) is centrifuged twice using acetone and ethanol, and then vacuum dried to obtain a powder of quantum dot particles. Afterwards, 30 g of the quantum dot particles are completely dissolved using 100 g of toluene, and 30 g of the compound of the following formula 2-1 is added thereto. Afterwards, the reaction was performed for 15 hours while maintaining 50°C in a nitrogen atmosphere to prepare quantum dot particles containing a ligand on the surface.

[Formula 2-1]

Synthesis Example 2: A-2

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that a compound represented by Formula 2-5 below was used instead of the compound represented by Formula 2-1.

[Formula 2-5]

Synthesis Example 3: A-3

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by Formula 2-7 below was used instead of the compound represented by Formula 2-1.

[Formula 2-7]

Synthesis Example 4: A-4

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that a compound represented by Formula 2-11 below was used instead of the compound represented by Formula 2-1.

[Formula 2-11]

Synthesis Example 5: A-5

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that a compound represented by Formula 2-17 below was used instead of the compound represented by Formula 2-1.

[Formula 2-17]

Synthesis Example 6: A-6

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by Formula 3 below was used instead of the compound represented by Formula 2-1.

[Formula 3]

Synthesis Example 7: A-7

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that a compound represented by Formula 4 below was used instead of the compound represented by Formula 2-1.

[Formula 4]

Synthesis Example 8: A-8

Quantum dot particles containing a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that a compound represented by Formula 5 below was used instead of the compound represented by Formula 2-1.

[Formula 5]

Examples and Comparative Examples

(1) Preparation of photosensitive resin composition

A photosensitive resin composition was prepared by mixing the components listed in Table 1 below in the corresponding amounts (% by weight).

division
(weight%) quantum dot particles binder resin polymerizable compound polymerization initiator menstruum Example 1 15
(A-1) 10 1.6 0.1 73.3 Example 2 15
(A-2) 10 1.6 0.1 73.3 Example 3 15
(A-3) 10 1.6 0.1 73.3 Example 4 15
(A-4) 10 1.6 0.1 73.3 Example 5 15
(A-5) 10 1.6 0.1 73.3 Comparative Example 1 15
(A-6) 10 1.6 0.1 73.3 Comparative Example 2 15
(A-7) 10 1.6 0.1 73.3 Comparative Example 3 15
(A-8) 10 1.6 0.1 73.3

The specific ingredient names listed in Table 1 are as follows.

Quantum dot particles (A)

1) A-1: Quantum dot particles prepared in Synthesis Example 1

2) A-2: Quantum dot particles prepared in Synthesis Example 2

3) A-3: Quantum dot particles prepared in Synthesis Example 3

4) A-4: Quantum dot particles prepared in Synthesis Example 4

5) A-5: Quantum dot particles prepared in Synthesis Example 5

6) A-6: Quantum dot particles prepared in Synthesis Example 6

7) A-7: Quantum dot particles prepared in Synthesis Example 7

8) A-8: Quantum dot particles prepared in Synthesis Example 8

Binder Resin (B)

Acrylic binder resin (SPCY-1L, manufactured by Showa Polymers)

Polymerizable Compound (C)

Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D)

Irgaqure-907 (manufactured by BASF)

Solvent (E)

Propylene glycol monomethyl ether acetate (PGMEA)

(2) Manufacturing of curly filter

After applying the photosensitive resin composition according to Examples and Comparative Examples on a glass substrate by spin coating, it was placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. A test photomask having a square transmission pattern of 20mm The ultraviolet light source used was an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio Denki Co., Ltd.) and irradiated light at an exposure dose (365 nm) of 200 mJ/cm ² in an atmospheric atmosphere. Afterwards, the thin film was developed by immersing it in an aqueous KOH solution of pH 10.5 for 80 seconds.

Afterwards, it was washed with distilled water, dried by blowing nitrogen gas, and heated in an oven at 150°C for 10 minutes to prepare a color filter. The pattern thickness of the manufactured color filter was 3.0 μm.

Experiment example

(1) Evaluation of dispersibility of quantum dot particles

The quantum dot particles prepared in Synthesis Examples 1 to 8 were dispersed in PGMEA (Propylene Glycol, Mono Methyl, Ether, Acetate) solvent to prepare a quantum dot dispersion solution containing 50% by weight of solid content. Afterwards, the particle size of the prepared quantum dot dispersion solution was measured using a particle size analyzer. The lower the dispersibility, the larger the particle size of the quantum dots may be due to agglomeration. The evaluation results are shown in Table 2 below.

division Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 particle size
(nm) 11 10 13 9 10 2400 19 16

Referring to Table 2, it can be seen that in the case of Synthesis Examples 1 to 5 containing ligands according to exemplary embodiments, the particle size of the quantum dot particles in the dispersion solution is low, and accordingly, it can be predicted that the dispersibility of the quantum dot particles is excellent. You can.

On the other hand, in the case of Synthesis Example 6, which includes a ligand with a general alkyl chain structure, it can be seen that the particle size is very high, and accordingly, it can be seen that the dispersibility in a polar organic solvent such as PGMEA is deteriorated.

In the case of Synthesis Examples 7 and 8 containing a ligand having a linear ether group, it can be confirmed that the particle size is somewhat higher than that of Synthesis Examples 1 to 5.

(2) Storage stability evaluation

The photosensitive resin compositions according to Examples and Comparative Examples were left at room temperature, and the viscosity over time was measured using a viscometer (manufactured by Brookfield). There is little change in viscosity over time, and the lower the viscosity, the better the storage stability. The evaluation results are shown in Table 3 below.

(3) Evaluation of light efficiency and light durability

Light efficiency was calculated by irradiating blue light to the manufactured color filter and measuring the degree of conversion to green light. Light efficiency was measured using QE-2000 (manufactured by Otsuka), and as blue light of 450 nm was applied to the color filter, all green light emitted in all directions was absorbed and calculated as an integral value. Light efficiency was calculated as a percentage of the increase in the peak converted to green light compared to the decrease in the blue light absorption peak.

In addition, after the color filter was left in a blue light source at room temperature for 7 days, the light efficiency was measured and the decrease was calculated. Since light efficiency decreases due to oxidation of quantum dot particles, light durability can be confirmed by measuring light efficiency after leaving. Light durability was expressed as a percentage of the ratio of light efficiency after neglect to initial light efficiency. Higher light durability means superior oxidation stability.

The evaluation results are shown in Table 3 below.

division storage stability
(viscosity, cp) light efficiency
(%) optical durability
(%) Early 2 weeks 4 weeks Early After neglect Example 1 10.1 10.8 11.1 71 63 88.7 Example 2 10.7 11.3 11.5 75 67 89.3 Example 3 11.0 11.5 11.7 70 59 84.2 Example 4 10.5 11.1 11.5 78 72 92.3 Example 5 10.8 11.3 11.6 80 73 91.2 Comparative Example 1 11.1 12.0 13.2 40 22 55.0 Comparative Example 2 11.4 12.5 13.5 48 29 60.4 Comparative Example 3 11.0 11.8 12.1 44 29 65.9

Referring to Table 3, it can be seen that the change in viscosity over time is small in the case of color filters manufactured using photosensitive resin compositions according to exemplary embodiments. In addition, it can be confirmed that the initial light conversion rate is high and the light durability is excellent as oxidation of the quantum dot particles is prevented.

On the other hand, in Comparative Examples 1 to 3, it can be seen that the change in viscosity over time is large as the storage stability is deteriorated. The initial light conversion rate is low, and it can be seen that the light conversion rate decreases significantly over time.

Claims (13)

A photosensitive resin composition comprising quantum dot particles containing a ligand having a thiol group and a tetrahydrofuranyl group.
delete The photosensitive resin composition of claim 1, wherein the quantum dot particles include a ligand represented by the following formula (1):
[Formula 1]

(In Formula 1 above,
L is a divalent hydrocarbon group that may contain a carbonyl group,
The divalent hydrocarbon group is a substituted or unsubstituted alkylene group having 1 to 13 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 13 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms. selected from the group consisting of a cycloalkylene group having 3 to 13 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 13 carbon atoms, and a substituted or unsubstituted cycloalkynylene group having 3 to 13 carbon atoms,
n is an integer from 0 to 10).
The photosensitive resin composition of claim 1, wherein the quantum dot particles include at least one selected from the group consisting of ligands represented by the following formulas 2-1 to 2-19:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]
.
The photosensitive resin composition of claim 1, wherein the quantum dot particles include at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, or a compound containing the same. .
The photosensitive resin composition of claim 1, wherein the quantum dot particles include a core and a shell covering the core.
The photosensitive resin composition of claim 6, wherein the core includes indium (In) and phosphorus (P), and the shell includes zinc (Zn), selenium (Se), and sulfur (S).
The method of claim 6, wherein the shell includes a first shell layer covering the core and a second shell layer covering the first shell layer,
The photosensitive resin composition, wherein the core includes InP or InZnP, the first shell layer includes ZnSe or ZnSeS, and the second shell layer includes ZnS.
The photosensitive resin composition of claim 1, wherein the photosensitive resin composition further includes at least one of a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.
A photocurable pattern formed from a photosensitive resin composition containing quantum dot particles containing a ligand having a thiol group and a tetrahydrofuranyl group.
An image display device comprising a photocurable pattern formed from a photosensitive resin composition including quantum dot particles including a ligand having a thiol group and a tetrahydrofuranyl group.
Quantum dot particles in which a ligand having a thiol group and a tetrahydrofuranyl group is bound to the surface.
The method of claim 12, wherein the ligand is a quantum dot particle represented by the following formula 1:
[Formula 1]

(In Formula 1 above,
L is a divalent hydrocarbon group that may contain a carbonyl group,
The divalent hydrocarbon group is a substituted or unsubstituted alkylene group having 1 to 13 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 13 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 13 carbon atoms. selected from the group consisting of a cycloalkylene group having 3 to 13 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 13 carbon atoms, and a substituted or unsubstituted cycloalkynylene group having 3 to 13 carbon atoms,
n is an integer from 0 to 10).