TW201825649A - Self-emissive photosensitive resin composition, and color filter and image display device prepared using the same - Google Patents

Abstract

Disclosed is a self-emissive photosensitive resin composition, including quantum dots and scattering particles, wherein the scattering particles include a first metal oxide having an average particle diameter of 100 to 500 nm and a second metal oxide having an average particle diameter of 30 to 500 nm, wherein the first metal oxide is TiO2 and the second metal oxide is ZnO.

Description

Self-luminous photosensitive resin composition, and color filter and image display device prepared using the same

The invention relates to a self-emissive photosensitive resin composition, which includes specific scattering particles, a color filter applied thereto, and an image display device applied thereto.

A color filter is a thin-film optical component that can extract three red, green, and blue colors of fine pixel units from white light to achieve color. The size factor of a pixel is ten to several hundred micrometers. In this color filter, a black matrix layer is formed on a transparent substrate in a predetermined pattern to shield a boundary portion between each pixel. portion). The three primary colors (usually red (R), green (G), blue (B)) of a plurality of colors are arranged in a predetermined pattern to form a pixel portion in which each pixel is stacked in order.

Recently, as a method for implementing a color filter, a pigment dispersion method using a photosensitive resin of a pigment dispersion type has been used. However, when the light emitted by a light source passes through a color filter, the color filter absorbs a part of the light, thereby reducing the luminous efficiency, and the color reproduction is deteriorated due to the characteristics of the pigment contained in the color filter. Color reproduction.

Since a color filter is used in various fields including various image display devices, in addition to excellent pattern characteristics, performance (such as high color reproducibility, superior brightness, and high contrast) is particularly required. Therefore, in order to solve this problem, a method for preparing a color filter using a self-emissive photosensitive resin composition containing quantum dots is proposed.

However, due to the nanoscale size of quantum dots, quantum dots are innate non-scattering particles. Therefore, when light passes through a color filter containing quantum dots, compared to the case of other dyes or pigments, the light passes through a shorter optical path. Therefore, unless the color filter is thick enough, the quantum dots will absorb most of the light. To solve this problem, a method using scattering particles is proposed. However, the absorption of light by scattering particles will reduce the luminous efficiency.

The Korean Patent Application No. 10-2012-0131071 relates to an optical member and a display device including the same, and provides an optical member including a host layer. A plurality of wavelengths of the particles and a plurality of inorganic particles arranged in the main layer. However, the above-mentioned invention is difficult to achieve improvement in light emission efficiency.

Korean Patent Application Publication No. 10-2010-0037283 relates to a liquid crystal display device and a method for preparing the same, and provides a liquid crystal display device including a transparent light diffusion layer formed of a transparent polymer. The transparent polymer includes a plurality of transparent beads. However, since the size of the transparent beads is large, the quality of a paint film may be deteriorated.

Therefore, there is a need to develop scattering particles that can be applied to high-reliability panels by improving luminous efficiency and increasing light retention rate.

(Patent Document 1) Korean Patent Application Publication No. 2012-0131071 (December 4, 2012) (Patent Document 2) Korean Patent Application Publication No. 2010-0037283 (April 9, 2010)

An object of the present invention is to provide a self-emissive photosensitive resin composition having excellent color reproducibility and high light retention rate.

Another object of the present invention is to provide a color filter and an image display device prepared with a self-luminous photosensitive resin composition and having excellent luminous efficiency, high light retention, or excellent reflective luminance.

To solve the above problems, according to an aspect of the present invention, a self-luminous photosensitive resin composition including quantum dots and scattering particles is provided, wherein the scattering particles include a first particle having an average particle diameter of 100 to 500 nanometers (nm). A metal oxide and a second metal oxide having an average particle diameter of 30 to 500 nanometers (nm), wherein the first metal oxide is titanium dioxide (TiO ₂ ) and the second metal oxide is zinc oxide ( ZnO).

According to another aspect of the present invention, a color filter having a cured product of a self-luminous photosensitive resin composition is provided.

According to another aspect of the present invention, an image display device including the color filter is provided.

The present invention will be described in more detail below.

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

In the present invention, it should be understood that, unless stated otherwise, when a part “comprises” any element, this part may include other elements without excluding other elements.

<Self-emissive photosensitive resin composition>

One aspect of the present invention relates to a self-luminous photosensitive resin composition including quantum dots and scattering particles, wherein the scattering particles include a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and a first metal oxide having 30 A second metal oxide with an average particle diameter of 500 nanometers (nm), wherein the first metal oxide is titanium dioxide (TiO ₂ ) and the second metal oxide is zinc oxide (ZnO).

Quantum dot

The quantum dots included in the self-luminous photosensitive resin composition of the present invention are nanoscale semiconductor materials. Atoms form a molecule, and molecules form an assembly of small molecules called a cluster to form nano particles. Especially when nano particles have semiconductor characteristics, these nano particles are called quantum dots. When quantum dots reach an excited state by absorbing energy from the outside, these quantum dots have a characteristic of releasing energy corresponding to an energy band gap. In summary, when the self-luminous photosensitive resin composition of the present invention includes quantum dots, the composition may be self-emissive.

In a conventional image display device including a color filter, white light passes through the color filter to achieve color. During this process, the color filter absorbs a part of the light and reduces the luminous efficiency. However, when an image display device includes a color filter prepared using the self-luminous photosensitive resin composition according to the present invention, the color filter is self-emit by light emitted from a light source. light), so excellent luminous efficiency can be achieved. In addition, due to the emission of colored light, color reproducibility is excellent, and because light is emitted in all directions by optical luminescence, the viewing angle can be improved.

The quantum dot is not particularly limited as long as the quantum dot can emit light by an optical stimulus. For example, one or more semiconductor compounds selected from group II-VI, group III-V semiconductor compounds, group IV-VI semiconductor compounds and group IV elements or compounds including group IV elements can be used as quantum dots. .

One or more types of the group II-VI semiconductor compounds may be selected from the group consisting of a binary compound, a ternary compound, and a quaternary compound. The binary compound is selected from the group consisting of cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), and zinc oxide (ZnO ), Mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe), and mixtures thereof. The ternary compound is selected from the group consisting of cadmium selenium sulphur (CdSeS), cadmium selenium tellurium (CdSeTe), cadmium selenium tellurium (CdSTe), zinc selenium sulfide (ZnSeS), zinc selenium tellurium (ZnSeTe), zinc sulfide tellurium (ZnSTe), mercury selenium Sulfur (HgSeS), HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgS (CdHgSe), cadmium mercury tellurium (CdHgTe), mercury zinc sulphur (HgZnS), mercury zinc selenium (HgZnSe), mercury zinc tellurium (HgZnTe) and mixtures thereof. This quaternary compound is selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSeTe, and CdHgSeTe (CdHgSTe), HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

One or more types of the III-V semiconductor compounds may be selected from the group consisting of a binary compound, a ternary compound, and a quaternary compound. The binary compound is selected from the group consisting of gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), aluminum nitride (AlN), aluminum phosphide (AlP), and arsenide A group consisting of aluminum (AlAs), aluminum antimonide (AlSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), and mixtures thereof. The ternary compound is selected from the group consisting of gallium nitride phosphorus (GaNP), gallium nitride arsenic (GaNAs), gallium nitride antimony (GaNSb), gallium phosphorus arsenic (GaPAs), gallium phosphorus antimony (GaPSb), aluminum nitrogen phosphorus (AlNP), aluminum nitrogen Arsenic (AlNAs), Aluminum Nitrogen Antimony (AlNSb), Aluminum Phosphorus Arsenic (AlPAs), Aluminum Phosphorus Antimony (AlPSb), Indium Nitrogen Phosphorus (InNP), Indium Nitrogen Arsenic (InNAs), Indium Nitrogen Antimony (InNSb), Indium Phosphorus Arsenic (InPAs), indium phosphorus antimony (InPSb), and mixtures thereof. This quaternary compound is selected from the group consisting of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInPS (GaInNP), GaInNAs, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNPs, InAlNAs ), InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

One or more types of the group IV-VI semiconductor compounds may be selected from the group consisting of a binary compound, a ternary compound, and a quaternary compound. The binary compound is selected from the group consisting of tin sulfide (SnS), tin selenide (SnSe), tin telluride (SnTe), lead sulfide (PbS), lead selenide (PbSe), lead telluride (PbTe), and mixtures thereof. Groups of people. This ternary compound is selected from the group consisting of tin selenosulfur (SnSeS), tin selenotellurium (SnSeTe), tin thiotellurium (SnSTe), lead selenium sulfide (PbSeS), lead selenotellurium (PbSeTe), lead sulfide (PbSTe), tin lead Group consisting of sulfur (SnPbS), tin-lead selenium (SnPbSe), tin-lead tellurium (SnPbTe), and mixtures thereof. The quaternary compound is selected from the group consisting of tin lead selenium selenium (SnPbSSe), tin lead selenium tellurium (SnPbSeTe), tin lead selenium tellurium (SnPbSTe), and mixtures thereof.

One or more types of Group IV elements or compounds including them may be selected from the group consisting of elemental compounds and a binary compound. This elemental compound is selected from the group consisting of silicon, germanium, and mixtures thereof. The binary compound is selected from the group consisting of silicon carbide (SiC), silicon germanium (SiGe), and mixtures thereof, and is not limited thereto.

The quantum dot may have a homogeneous single structure, a dual structure such as a core-shell structure, a gradient structure, etc., or a mixed structure thereof ). For example, in the core-shell structure, each material constituting a core and a shell may be made of the aforementioned different semiconductor compounds. More specifically, the core may include one or more materials selected from the group consisting of cadmium selenide (CdSe), cadmium sulfide (CdS), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium telluride (CdTe), The group consisting of cadmium selenium tellurium (CdSeTe), cadmium zinc sulfur (CdZnS), lead selenide (PbSe), silver indium zinc sulfide (AgInZnS), and zinc oxide (ZnO) is not limited thereto. The shell may include one or more materials selected from the group consisting of cadmium selenide (CdSe), zinc selenide (ZnSe), zinc sulfide (ZnS), zinc telluride (ZnTe), cadmium telluride (CdTe), and lead sulfide (PbS ), Titanium oxide (TiO), strontium selenide (SrSe), and mercury selenide (HgSe) are not limited thereto.

A coloring photosensitive resin composition used to prepare a typical color filter includes red, green, and blue colorants to achieve color implementation. In addition, photoluminescence quantum dots can be classified into red quantum dots, green quantum dots, and blue quantum dots. In short, the quantum dots according to the present invention may be red quantum dots that emit red light, green quantum dots that emit green light, and blue quantum dots that emit blue light.

Quantum dots can be synthesized by a wet chemical process, a metal-organic chemical vapor deposition (MOCVD) method, or a molecular beam epitaxy (MBE) method. To synthesize, not limited to this.

The wet chemical method is a method of growing particles by adding a precursor material to an organic solvent. As the crystal grows, the organic solvent naturally coordinates with the surface of the quantum dot crystals and acts as a dispersant to control the crystal growth. Therefore, compared with vapor deposition (such as metal-organic chemical vapor deposition) or molecular beam epitaxy, the growth of nano particles can be controlled by a simpler and less expensive method. Therefore, it is preferable to use a wet chemical method to prepare a quantum dot according to the present invention.

The invention does not specifically limit the content of quantum dots. The content of the quantum dots is 3 to 80 parts by weight, and preferably 5 to 70 parts by weight, with respect to 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. When the included quantum dots are within the above range, the light emitting efficiency is excellent and a pixel pattern can be easily formed. When the included quantum dots are lower than the above range, the luminous efficiency may be insufficient. When the content of the quantum dot exceeds the above range, it may be difficult to form a pixel pattern because the content of other components is insufficient. Therefore, it is preferable to satisfy the above range.

Scattering particles

The scattering particles according to the present invention are used to increase the luminous efficiency of a color filter. Generally speaking, light emitted by a light source is incident on a color filter at a critical angle. At this time, the incident light or self-emitting light emitted by the quantum dot collides with the scattering particles to increase a light path, thereby increasing luminescence intensity. Therefore, the luminous efficiency of this color filter can be improved.

The scattering particles according to the present invention include a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and a second metal oxide having an average particle diameter of 30 to 500 nanometers (nm). The first metal oxide is titanium dioxide and the second metal oxide is zinc oxide.

In the present invention, the "average particle diameter" means a number of an average particle diameter. For example, a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (transmission electron microscope, TEM) to obtain an average particle size. Specifically, several samples are extracted from an image observed by FE-SEM or TEM, and the diameters of these samples are measured to obtain an arithmetic mean.

The scattering particles according to the present invention include a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and a second metal oxide having an average particle diameter of 30 to 500 nanometers (nm), and Contains titanium dioxide as the first metal oxide and zinc oxide as the second metal oxide. Therefore, when scattering particles are used, a color filter having excellent light emission intensity and excellent reflection brightness can be prepared.

When the self-luminous photosensitive resin composition includes the first metal oxide, the effect of the oxide is to increase the luminescence retention rate so that the brightness can be sufficiently maintained.

In addition, when the self-luminous photosensitive resin composition includes this second metal oxide having an average particle diameter of 30 to 500 nanometers (nm), light scattering can be sufficiently induced and an optical path can be increased, thereby improving light emission intensity, and A color filter with high brightness and high light retention can be prepared.

When the average particle diameter of the scattering particles is smaller than the above range (for example, 10 nanometers (nm)), the effect of scattering incident light or the effect of light emitted by quantum dots may not be achieved. When the average particle diameter of the scattering particles exceeds the above range, the scattering particles may become too large. When the particles are arranged in a composition, the surface of a self-emissive layer may be uneven.

In the present invention, the first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and the second metal oxide having an average particle diameter of 30 to 500 nanometers (nm) are commonly used as scattering particles. The first metal oxide includes titanium dioxide and the second metal oxide includes zinc oxide. Therefore, the brightness can be improved and the oxidation of quantum dots during a post bake (PB) process can be effectively prevented, thereby preventing the brightness from decreasing between processes.

In one embodiment of the present invention, a ratio of an average particle diameter of the second metal oxide to an average particle diameter of the first metal oxide may be 0.1 to 0.5. Specifically, for the scattering particles, it is preferable to use a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm), and more preferably 150 to 400 nanometers (nm). In this case, the average particle diameter of the second metal oxide is preferably 0.1 to 0.5 times the average particle diameter of the first metal oxide.

In another embodiment of the present invention, when the average particle diameter of the second metal oxide is not larger than the average particle diameter of the first metal oxide, uniform mixing is feasible, so as to make the surface of a self-emitting layer uniform. Specifically, in another embodiment of the present invention, the difference between the average particle diameter of the first metal oxide and the average particle diameter of the second metal oxide may be 60 nanometers (nm) or more.

In another embodiment of the present invention, the scattering particles further include oxides of one or more of these metals. Lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium ( Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), scandium (Sc), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel ( Ni), copper (Cu), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), molybdenum (Mo), cesium (Cs), barium (Ba), lanthanum ( La), Hafnium (Hf), Tungsten (W), Hafnium (Tl), Lead (Pb), Cerium (Ce), Hafnium (Pr), Neodymium (Nd), Hafnium (Pm), Hafnium (Sm), Hafnium ( Eu), gadolinium (Gd), gadolinium (Tb), gadolinium (Dy), '(Ho), gadolinium (Er), gadolinium (Tm), gadolinium (Yb), antimony (Sb), tin (Sn), zirconium ( Zr), niobium (Nb), tantalum (Ta) and indium (In).

In another embodiment of the present invention, the metal oxide may further be one or more types selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ), and zirconium dioxide (ZrO ₂ ), barium titanate (BaTiO ₃ ), tantalum pentoxide (Ta ₂ O ₅ ), trititanium pentoxide (Ti ₃ O ₅ ), indium tin oxide (ITO), indium zinc oxide (IZO), arsenic trioxide (ATO ), Zinc oxide-aluminum (ZnO-Al), niobium trioxide (Nb ₂ O ₃ ), tin oxide (SnO), and magnesium oxide (MgO). When necessary, a compound (such as an acrylate) having an unsaturated bond can be used to surface-treated a metal oxide.

In another embodiment of the present invention, 50 to 90 parts by weight of the first metal oxide and not less than 10 to less than 50 parts by weight of the second metal may be present with respect to 100 parts by weight of the total solid content of the scattering particles. Oxide. When the first metal oxide and the second metal oxide satisfy the respective ranges, the light retention rate may be increased and the brightness may be prevented from decreasing. When the first metal oxide is present in an amount smaller than the above range, the increase in light retention may be insufficient. When the first metal oxide is present in an amount exceeding the above range, a scattering effect may be reduced, thereby reducing brightness. Therefore, it is preferable to use this first metal oxide in an amount within the above range. When the amount of this second metal oxide is less than the above range, light scattering may not be performed properly, and the improvement in brightness may be insufficient. When the second metal oxide is present in an amount exceeding the above range, the light retention rate may be reduced. Therefore, it is preferable to use this second metal oxide in an amount within the above range.

The content of the scattering particles in a total composition may be limited to sufficiently improve the luminous intensity of a color filter. Specifically, in another embodiment of the present invention, the scattering particles may be contained in an amount of 0.1 to 50 parts by weight, and preferably 0.3 to 30 parts by weight, relative to 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. When the amount of the scattering particles is within the above range, a color filter having excellent luminous intensity and stable performance can be prepared. When the scattering particles are present in an amount smaller than the above range, it may be difficult to obtain a desired luminous intensity. When the amount of the scattering particles exceeds the above range, the increase in the luminous intensity may be insufficient, and the stability of the self-luminous photosensitive resin composition including the scattering particles may be reduced. Therefore, it is preferable to use an amount of scattering particles within the above range.

In another embodiment of the present invention, the self-luminous photosensitive resin composition may further include one or more types selected from the group consisting of photopolymerizable compounds, alkali-soluble resins, and photopolymerization. A group of photopolymerization initiators and solvents.

Photopolymerizable compound

The self-luminous photosensitive resin composition according to the present invention may include a photopolymerizable compound. This photopolymerizable compound is a compound that can be polymerized by an active group, an acid, and the like produced by a photopolymerization initiator described below. Such photopolymerizable compounds may include monofunctional monomers, bifunctional monomers, multifunctional monomers having three or more functional groups, or the like.

Examples of the monofunctional monomer may include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethyl acrylate 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone or the like, and its commercial products may include Aronix M-101 (TOAGOSEI Co.), Kayarad TC-110S (NIPPON KAYAKU Co.), Viscoat 158 (OSAKA YUKI KAGAKU KOGYO Co.) and similar Things are not limited to this.

Examples of the difunctional monomer may include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate ( 1,6-hexanediol di (meth) acrylate), ethyleneglycol di (meth) acrylate, neoopentylglycol di (meth) acrylate , Triethyleneglycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methyl 3-methylpentanediol di (meth) acrylate and the like, and its commercial products may include Aronix M-210, M-1100, 1200 (TOAGOSEI Co.) , Kayarad HDDA (NIPPON KAYAKU Co.), Viscoat 260 (OSAKA YUKI KAGAKU KOGYO Co.), AH-600, AT-600 or UA-306H (Kyoei KYOEISHA KAGAKU Co.) and the like are not limited thereto.

Examples of the polyfunctional monomer having three or more functional groups may include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate ) Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaerythritol (Meth) acrylate (dipentaerythritol penta (meth) acrylate), ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate Ester (propoxylated dipentaerythritol hexa (meth) acrylate), dipentaerythritol hexa (meth) acrylate hexa (meth) acrylate) and the like, and its commercial products may include Aronix M-309, TO-1382 (TOAGOSEI Co.), Kayarad TMPTA, Kayarad DPHA or Kayarad DPHA-40H (NIPPON KAYAKU Co.) and the like are not limited to this.

In addition, the photopolymerizable compound may be dipentaerythritol (poly) acrylate having a hydroxyl group or a carboxylic acid group as shown in the following Chemical Formulae 1 to 2.

Chemical formula 1

In Chemical Formula 1, R ₁ is an acrylate group or a methacrylate group, and R ₂ is a hydrogen, an acrylyl group, or a methacryloyl group. group).

Chemical formula 2

In Chemical Formula 2, R ₃ to R ₅ are the same or different, and R ₃ to R ₅ are each OH, a monoalkyl group having 1 to 4 carbon atoms, a monoacrylate group, a methacrylate group, or -OR. ₇ . In this case, at least one of R ₃ to R ₅ is an acrylate group or a methacrylate group, and R ₇ is . Here, R ₆ is -C (= O) CH ₂ CH ₂ C (= O) OH; R ₈ and R ₉ are each an acrylate group or a methacrylate group; R ₁₀ is hydrogen, or acrylidine Group, monomethacryl group or -C (= O) CH ₂ CH ₂ C (= O) OH.

For the photopolymerizable compound of the present invention, a polyfunctional monomer having two or more functional groups can be used. More preferably, a pentafunctional photopolymerizable compound containing a carboxylic acid group can be used. When a polyfunctional monomer having five or more functional groups is used, an excellent one-pixel pattern is formed. In the case of a polyfunctional monomer including a carboxylic acid group and having five or more functional groups, the decrease in brightness due to the polymerization of quantum dot particles can be particularly prevented. Due to the excellent light reactivity, a pixel pattern with excellent brightness can be formed.

The photopolymerizable compound may be contained in an amount of 5 to 70 parts by weight, and preferably 7 to 65 parts by weight, with respect to 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. When the photopolymerizable compound is present in an amount within the above range, the strength or smoothness of a pixel portion can be improved. When the photopolymerizable compound is present in an amount smaller than the above range, the degree of photo-curing by light may decrease, and it may be difficult to form a pixel pattern. When the photopolymerizable compound is present in an amount exceeding the above range, pattern peeling may occur.

Alkali soluble resin

The self-luminous photosensitive resin composition of the present invention may include an alkali-soluble resin. The alkali-soluble resin imparts a component of an alkali developing solution having a solubility to an alkaline developing solution used in a developing process. In other words, the alkali-soluble resin can help the unexposed portion of a photosensitive resin layer formed using a self-luminous photosensitive resin composition to be alkali-soluble. In the present invention, any resin dissolved in an alkaline developing solution can be used as the alkali-soluble resin, and is not particularly limited.

Specifically, the alkali-soluble resin can be prepared by copolymerizing one or more types selected from an unsaturated monomer having a carboxyl group and a monomer having an unsaturated bond copolymerizable therewith, and is not limited thereto. Unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids, and the like can be used as the unsaturated monomer having a carboxyl group.

Specific examples of this unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of this unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, pyrocitric acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be a monoanhydride, and specific examples thereof may include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acid may be mono (2-methacryloyloxyalkyl) ester, and may include, for example, succinic acid mono (2-propenyloxyalkyl) ester. (Succinic acid mono (2-acryloyloxyethyl)), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl) (Phthalic acid mono (2-acryloyloxyethyl)), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate having dicarboxylic polymers at both ends, for example, may include ω-carboxy polycaprolactone monoacrylate (ω-carboxypolycaprolactone monoacrylate), ω-carboxypolycaprolactone monomethacrylate, and the like. These carboxyl groups containing unsaturated monomers may be used alone or in a combination of two or more of them.

In addition, the monomer having an unsaturated bond which can be copolymerized with an unsaturated monomer having a carboxyl group may include one or more species selected from aromatic vinyl compounds, unsaturated carboxylic acid Unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkylester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl carboxylate compounds (carboxylic acid vinyl ester compounds), unsaturated ether compounds (vins cyanide compounds), unsaturated amide compounds (unsaturated imide compounds), unsaturated imide compounds (unsaturated ether compounds), Aliphatic conjugated diene compounds, macromonomers with a monoacryloyl group or a monomethacryloyl group at the end of a molecular chain 、 Bulk monomer com pounds) and the like.

More specifically, the monomer having an unsaturated bond that can be copolymerized with an unsaturated monomer having a carboxyl group may include an aromatic vinyl compound such as styrene, α-methylstyrene ), O-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, ortho-methoxy O-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, o-vinylbenzylmethylether, M-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylmethylether M-vinylbenzylglycidylether, p-vinylbenzylglycidylether, and indene.

Unsaturated carboxylic acid ester compounds, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate ( n-propyl acrylate), n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate (n- butyl acrylate), n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl methacrylate butyl acrylate), sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate (2- hydroxyethyl acrylate), 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy Propyl acrylate (3-hyd roxypropyl acrylate), 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate), allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, Cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxymethyl 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacryl ate), methoxydiethyleneglycol acrylate, methoxydiethyleneglycol methacrylate, methoxytriethyleneglycol acrylate, methoxydiethyleneglycol methacrylate Triethylene glycol methacrylate (methoxytriethyleneglycol methacrylate), methoxypropyleneglycol acrylate, methoxypropyleneglycol methacrylate, methoxydipropyleneglycol acrylate , Methoxydipropyleneglycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiene Dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl propylene 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monoacrylate Glycerol monomethacrylate.

Unsaturated carboxylic acid aminoalkyl ester compounds, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminoacrylic acid 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylamino 3-dimethylaminopropyl methacrylate.

Unsaturated carboxylic acid glycidyl ester compounds, such as glycidyl acrylate and glycidyl methacrylate.

Vinyl carboxylate compounds, such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.

Unsaturated ether compounds, such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether.

Acrylonitrile compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide.

Unsaturated ammonium compounds such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2 -N-2-hydroxyethylmethacrylamide.

Unsaturated fluorenimine compounds such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Imine (N-cyclohexylmaleimide).

Aliphatic conjugated dienes, such as 1,3-butadiene, isoprene, and chloroprene.

Macromonomers with a single acrylyl group or a monomethacryl group at the end of the molecular chain of the polymer, including polystyrene, polymethyl acrylate, polymethacrylic acid Polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate and polysiloxane.

Bulk monomers, for example, a monomer having a norbornyl skeleton capable of reducing the dielectric constant, a monomer having an adamantane skeleton, and a rosin skeleton Monomers and the like.

When an alkali-soluble resin is used in a color filter, in order to improve the surface hardness, the weight-average molecular weight of the alkali-soluble resin is preferably in the range of 3,000 to 200,000, more in the range of 5,000 to 100,000, based on polystyrene. In addition, the molecular weight distribution (M _w / M _n ) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the weight-average molecular weight and molecular weight distribution of the alkali-soluble resin are within the above ranges, the surface hardness and resolution can be improved, and a non-exposed portion of a thin film in a developing solution can be added. Film remaining ratio and solubility.

The acid value of the alkali-soluble resin is preferably 20 to 200 milligrams (mg) of potassium hydroxide (KOH) per gram (g) relative to the solid content. The acid value indicates the amount of milligrams (mg) of potassium hydroxide required to neutralize 1 gram (g) of an acrylic polymer, and the acid value is related to the solubility of the polymer. When the acid value of the resin is within the above range, the solubility of the resin in a developing solution can be improved so that the non-exposed portion of the resin is more easily dissolved and the sensitivity is increased. Therefore, the residual ratio of the film can be improved due to the remaining pattern of an exposed portion during development.

The alkali-soluble resin is preferably contained in an amount of 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition.

When the amount of the alkali-soluble resin is within the above range, the solubility of the resin in a developing solution is sufficient and the degree of absence of a non-pixel portion is reduced. Therefore, it is difficult to generate debris on a substrate, and the film thickness of a pixel portion of an exposed portion during development is prevented from decreasing, thereby promoting pattern formation. When the amount of the alkali-soluble resin is less than the above range, the non-pixel portion may be missing. When the amount of the alkali-soluble resin exceeds the above range, the solubility of the resin in some developing solutions may be lowered and pattern formation may be somewhat difficult.

Photopolymerization initiator

When exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, an electron beam, and X-rays, a photopolymerization initiator included in the self-luminous photosensitive resin composition of the present invention can trigger the aforementioned A compound that undergoes polymerization by photopolymerization. During a reaction, the photopolymerization initiator has the characteristics of generating free radicals and the like.

Without reducing the extent of the object of the present invention, compounds commonly used in the art can be used as photopolymerization initiators. The type of the compound is not particularly limited as long as the compound is capable of polymerizing a binder with a photopolymerizable compound. As a typical example, triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, and oxime-based compounds can be used. Compounds) and the like are used as photopolymerization initiators, but are not limited thereto. One or more of these compounds can be selected and used.

The self-luminous photosensitive resin composition including a photopolymerization initiator is highly sensitized. The pixel portion of a color filter prepared using a self-luminous photosensitive resin composition has higher strength and can improve pattern formation. Therefore, it is preferable to include a photopolymerization initiator.

Specific examples of the triazine-based compound may include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine (2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine), 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine (2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine), 2,4-bis (trichloromethyl) -6-piperyl-1,3,5- Triazine (2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine), 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine (2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine), 2,4-bis (trichloromethyl) -6- [ 2- (5-methyl-2-furanyl) vinyl] -1,3,5-triazine (2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl ] -1,3,5-triazine), 2,4-bis (trichloromethyl) -6- [2- (2-furanyl) vinyl] -1,3,5-triazine (2,4 -bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine), 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine (2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine), 2,4-bis (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyl) vinyl]-1,3,5-triazine (2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5 -triazine) and the like, are not limited thereto.

Examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone (2-hydroxy-2-methyl-1-phenylpropan- 1-one), benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-acetone (2 -hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one), 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4- Methylphenylthio) -2-morpholinyl-1-acetone (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino- 1- (4-morpholinylphenyl) -1-butanone (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one), 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] -1-acetone (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one), 2- (4 -Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinylphenyl) -1-butanone (2- (4-methylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinophenyl) butan-1-one) and the like. In addition, a compound represented by the following Chemical Formula 3 may be included.

Chemical formula 3

In Chemical Formula 3, R ₁ to R ₄ each independently represent hydrogen, a halogen, OH, unsubstituted or a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or unsubstituted or substituted A napthyl group substituted with a monoalkyl group having 1 to 12 carbon atoms.

Examples of the compound represented by Chemical Formula 3 may include 2-methyl-2-amino (4-morpholinophenyl) -1-ethyl ketone (2-methyl-2-amino (4-morpholinophenyl) ethan-1- one), 2-ethyl-2-amino (4-morpholinophenyl) -1-ethyl ketone (2-ethyl-2-amino (4-morpholinophenyl) ethan-1-one), 2-propyl- 2-amino (4-morpholinylphenyl) -1-ethyl ketone (2-propyl-2-amino (4-morpholinophenyl) ethan-1-one), 2-butyl-2-amino (4-morpholine 2-phenyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) -1-acetone (2-methyl-2-amino (4-morpholinophenyl) propan-1-one), 2-methyl-2-amino (4-morpholinophenyl) -1-butanone (2-methyl-2-amino (4-morpholinophenyl) butan-1-one), 2-ethyl-2-amino (4-morpholinophenyl) -1-acetone (2-ethyl-2-amino (4-morpholinophenyl) propan-1- one), 2-ethyl-2-amino (4-morpholinophenyl) -1-butanone (2-ethyl-2-amino (4-morpholinophenyl) butan-1-one), 2-methyl- 2-methylamino (4-morpholinophenyl) -1-acetone (2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one), 2-methyl-2-dimethylamino ( 4-morpholinylphenyl) -1-acetone (2-methyl- 2-dimethylamino (4-morpholinophenyl) propan-1-one), 2-methyl-2-diethylamino (4-morpholinylphenyl) -1-acetone (2-methyl-2-diethylamino (4- morpholinophenyl) propan-1-one) and the like.

Examples of the biimidazole-based compound may include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (2,2'-bis (2-chlorophenyl)- 4,4 ', 5,5'-tetraphenyl biimidazole), 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole (2,2 '-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenyl biimidazole), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (Alkoxyphenyl) biimidazole (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole), 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole ), 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (2,2-bis (2,6- dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole), or the phenyl group at the 4,4 ', 5,5' position is replaced by a carboalkoxy group An imidazole compound and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (2,2'-bis (2-chlorophenyl) -4 is more preferably used , 4 ', 5,5'-tetraphenyl biimidazole), 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole (2,2 ' -bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole), or 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5 ' -Tetraphenyl-1,2'-biimidazole (2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole) and the like.

Examples of the oxime-based compound may include o-ethoxycarbonyl-α-oxyimino-1-phenyl-1-acetone (o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one), 1- [9- Ethyl-6- (2-methylbenzyl) -9H-3-carbazolyl] -ethanone-1- (oxy-acetamoxime) (1- [9-ethyl-6- (2- methylbenzoyl) -9H-carbazole-3-yl] -ethanone-1- (O-acetyloxime)), (Z) -2-((benzyloxy) imino) -1- (4- (phenylthio) ) Phenyl) -1-octanone ((Z) -2-((benzoyloxy) imino) -1- (4- (phenylthio) phenyl) octan-1-one), (E) -1-(((1 -(9-ethyl-6- (2-methylbenzylidene) -9H-3-carbazolyl) ethinyl) amino) oxy) ethanone ((E) -1-(((1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl) ethylidyne) amino) oxy) ethanone), (E) -1-(((1- (6- (4-((2 , 2-dimethyl-1,3-dioxolane-4-yl) methoxy) -2-methylbenzyl) -9-ethyl-9H-3-carbazolyl) (Amino) amino) oxy) ethanone ((E) -1-(((1- (6- (4-((2,2-dimethyl-1,3-dioxolan-4-yl) methoxy) -2-methylbenzoyl ) -9-ethyl-9H-carbazole-3-yl) ethylidyne) amino) oxy) ethanone) and the like. Its commercial products may include OXE-01, OXE-02, and the like (BASF Co.), without being limited thereto. In addition, the oxime-based compound may include a compound represented by the following Chemical Formulae 4 to 6.

Chemical formula 4

Chemical formula 5

Chemical formula 6

In addition, other commonly used photopolymerization initiators may be further used without reducing the extent of the object of the present invention. Specific examples of other photopolymerization initiators may include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds (anthracene-based compounds), other photopolymerization initiators and the like. These may be used alone or in a combination of two or more of them.

Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the benzophenone-based compound may include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-phenylbenzophenone, 4- 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone (3 , 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone), 2,4,6-trimethylbenzophenone (2,4,6-trimethylbenzophenone), 4'-bis (N, N' -Dimethylamino) -benzophenone (4'-di (N, N'-dimethylamino) -benzophenone) and the like.

Examples of the thioanthrone compound may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the anthracene-based compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like.

Other photopolymerization initiators may include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 10-butyl-2-chloroacridone ( 10-butyl-2-chloroacridone), 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate ), Titanocene compounds and the like.

The photopolymerization initiator preferably contains 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the solid content of the self-luminous photosensitive resin composition of the present invention. When the photopolymerization initiator is present in the above range, the self-luminous photosensitive resin composition is highly sensitive and can shorten the exposure time, and can improve productivity and maintain high resolution. In addition, the intensity of one pixel portion formed by using the self-luminous photosensitive resin composition of the present invention and the flatness of the surface of the pixel portion can be improved.

In addition, a photopolymerization initiator combined with a photopolymerization initiator adjuvant may be used to enhance the sensitivity of the self-luminous photosensitive resin composition of the present invention. When the self-luminous photosensitive resin composition of the present invention contains a photopolymerization starting aid, the sensitivity is further increased. When a color filter is formed using a composition containing a photopolymerization initiation aid, productivity can be improved.

For example, one or more species selected from amine compounds and carboxylic acid compounds can be used as photopolymerization initiation aids.

For example, the amine compound can include aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, and methyl 4-dimethylaminobenzoate ( methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl-4-diamine 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl-p-toluidine (N, N- dimethyl-para-toluidine), 4,4'-bis (dimethylamino) benzophenone (also known as Michler's ketone), 4,4 '-Bis (diethylamino) benzophenone (4,4'-bis (diethylamino) benzophenone) and the like. Preferably, aromatic amine compounds can be used as the amine compound.

For example, the carboxylic acid compound may include aromatic heteroacetic acids, such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid ), Methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid ), Chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl Glycine (N-naphthylglycine) and naphthoxyacetic acid.

The photopolymerization initiation aid is preferably contained in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the solid content of the self-luminous photosensitive resin composition. When the amount of the photopolymerization initiating adjuvant is within the above range, the sensitivity of the self-luminous photosensitive resin composition is further improved. When a color filter is formed using a composition containing a photopolymerization initiation aid, productivity can be improved.

Solvent

A solvent included in the self-luminous photosensitive resin composition according to the present invention may be any organic solvent commonly used in the art, as long as the organic solvent effectively dissolves other components containing the self-luminous photosensitive resin composition, there is no particular limit. For example, this solvent may include ethers, acetic acid, aromatic hydrocarbons, ketones, alcohols, esters, and the like. You can choose and use one or more of them without limitation.

Specific examples of the ether solvent may include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether ether), diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; and propylene glycol dialkyl ether (propylene glycol dialkyl ethers), such as propylene glycol monomethyl ether.

Specific examples of acetate solvents may include ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate Ethyl cellosolve acetate; alkylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; and alkoxyalkylacetates, such as methoxybutylacetate and methoxy Methoxypentylacetate.

Specific examples of the aromatic hydrocarbon solvent may include benzene, toluene, xylene, mesitylene, and the like.

Specific examples of the ketone solvent may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone ( cyclohexanone) and the like.

Specific examples of the alcohol solvent may include ethanol, propanol, butanol, hexanol, cyclohexanol, ethyleneglycol, glycerol, and the like.

Specific examples of the ester solvent may include esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; and cyclic esters, such as γ -Gamma-butyrolactone.

These solvents may be used alone or in a combination of two or more of them.

Among these solvents, an organic solvent having a boiling point of 100 to 200 ° C. is preferably used in terms of coating properties and drying properties. More preferably, alkylene glycol alkyl ether acetates; ketones; and esters such as ethyl 3-ethoxypropionate, 3-methyl Methyl methoxypropionate and the like were used as solvents.

These solvents may be used alone or in a combination of two or more of them.

In the present invention, the content of the solvent is not particularly limited. The solvent may contain 60 to 90 parts by weight, preferably 60 to 85 parts by weight, with respect to 100 parts by weight of the self-luminous photosensitive resin composition. It is suitable when the included solvent is in this content range, because when a coating system is used, such as a roll coater, a spin coater, a Spin & spin coater, a slit coater (often referred to as a die coater), an ink-jet printer, and the like This resin composition tends to exhibit better coating properties. When the content of the solvent is less than the above range, the coating performance will be reduced and the process may be difficult to perform. When the content of the solvent exceeds the above range, the performance of a color filter formed using a self-luminous photosensitive resin composition may be reduced.

additive

The self-luminous photosensitive resin composition according to the present invention may further include additives, such as fillers, other polymer compounds, pigment dispersing agents, adhesion promoters, and antioxidants, as required. ) Antioxidants, ultraviolet absorbents and anti-aggregation agents.

Specific examples of the filler may include glass, silica, alumina, and the like.

Specific examples of other polymer compounds may include thermosetting resins such as epoxy resin, maleimide resin, and the like; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyacrylic Polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like.

As the pigment dispersant, a commercially available surfactant can be used. For example, useful surfactants such as silicon-based, fluorine-based, ester-based, cationic, anionic, non-ionic (nonionic) amphoteric surfactants. These surfactants may be used alone or in a combination of two or more of them.

Examples of the surfactant may include polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid-modified polyesters. modified polyesters), tertiary amine-modified polyurethanes, polyethyleneimines and the like. In addition, products with the following product names can be used: KP (SHINETSU KAGAKU KOGYO Co.), POLYFLOW (KYOEISHA KAGAKU Co.), EFTOP (TOCHEM PRODUCTS Co.)), MEGAFAC (DAINIPPON INK KAGAKU KOGYO Co.), FLOURAD (SUMITOMO 3M Co.), ASAHI GUARD, SURFLON (ASAHI GLASS Co., Ltd. .)), SOLSPERSE (ZENECA Co.), EFKA (EFKA CHEM. Co.), PB 821 (AJINOMOTO Co.) and the like.

For example, adhesion promoters may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy (2-methoxyethoxy) ) silane), N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane), N- (2-aminoethyl)- N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane), 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylidine 3-methacryloxypropyltrimethoxysilane, 3-mercapto Trimethoxy Silane (3-mercaptopropyltrimethoxysilane) and the like. Specific examples of the antioxidant may include 2,2'-thiobis (4-methyl-6-t-butylphenol) (2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6 -2,6-di-t-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber may include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (2- (3-tert-butyl-2-hydroxy- 5-methylphenyl) -5-chlorobenzotriazole), alkoxybenzophenones and the like.

Specific examples of the anti-aggregating agent may include sodium polyacrylate and the like.

As long as it does not interfere with the efficacy of the present invention, those with ordinary knowledge in the art can appropriately add and use this additive within a range. For example, 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight may be used with respect to 100 parts by weight of the total self-luminous photosensitive resin composition, without being limited thereto.

＜ Color filter ＞

Another aspect of the present invention relates to a color filter prepared using the self-luminous photosensitive resin composition.

When the color filter of the present invention is applied to an image display device, the light is emitted by a light source of a display device and the luminous efficiency can be improved. In addition, due to the emission of colored light, color reproducibility is excellent, and because light is emitted in all directions by optical luminescence, a viewing angle can be improved.

Specifically, the color filter according to the present invention includes a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and a first metal oxide having an average particle diameter of 30 to 500 nanometers (nm). A two-metal oxide and a cured product of a self-luminous photosensitive resin composition. The first metal oxide is titanium dioxide (TiO ₂ ) and the second metal oxide is zinc oxide (ZnO). Therefore, this color filter has excellent light retention and excellent reflection brightness.

The color filter may include a substrate and a pattern layer formed on the substrate. This pattern layer may include a cured product of the self-luminous photosensitive resin composition according to the present invention.

The substrate may be a color filter itself, or may be a part of a color filter placed on a display device or the like, which is not particularly limited. For example, the substrate may include glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate. The polymer substrate may include polyethersulfone (PES), polycarbonate (PC), or the like.

The pattern layer includes a layer of the photosensitive resin composition of the present invention, and the pattern layer can be formed by using the photosensitive resin composition and exposing, developing, and thermal curing according to one Composition of a predetermined pattern.

The pattern layer formed using the self-luminous photosensitive resin composition may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, or a blue layer containing blue quantum dot particles. Pattern layer. During light irradiation, the red pattern layer can emit red light, the green pattern layer can emit green light, and the blue pattern layer can emit blue light. When this pattern layer is applied to an image display device described below, the emitted light of a light source is not particularly limited, but it is preferable to use a light source that emits blue light to obtain better color reproducibility.

In another embodiment of the present invention, the pattern layer may include one or more types selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. The pattern layer may include only two types of the red pattern layer, the green pattern layer, and the blue pattern layer. In this case, the pattern layer may further include a transparent pattern layer containing no quantum dot particles.

When only two types of pattern layers are provided, a light source corresponding to light emitted by the remaining pattern layers not included may be used. For example, when the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, blue light passes through the transparent pattern layer and the transparent pattern layer displays blue.

The color filter including the substrate and the pattern layer described above may further include a barrier layer formed between each pattern and a black matrix, but is not limited thereto. In addition, a protective film may be further formed on the pattern layer of the color filter.

<Image display device>

Another aspect of the present invention relates to an image display device including the color filter. The color filter of the present invention can be applied not only to a conventional liquid crystal display device, but also to various image display devices, such as an electroluminescent display device and a plasma display device. , And a field emission display device.

The image display device according to the present invention has excellent light emitting efficiency, thereby exhibiting high brightness. In addition, the image display device has excellent color reproducibility, excellent reflection brightness, and a wide viewing angle.

Hereinafter, the present invention will be described in detail by explaining an exemplary embodiment of the present invention. However, the present invention can be implemented in many different forms, and the present invention should not be limited by the embodiments set forth herein. These embodiments are provided to more fully describe the disclosure to those skilled in the art. In addition, hereinafter, "%" and "parts" respectively represent percentages and parts by weight unless otherwise stated.

Preparation example 1. Preparation of Photoluminescence Green Quantum Dot Particles A with CdSe (core) / ZnS (shell) (CdSe (core) / ZnS (shell)) Structure

Combine cadmium oxide (CdO) (0.4 millimolar (mmol)), zinc acetate (4 millimolar (mmol)), oleic acid (5.5 ml (mL)) and 1-octadecene (20 ml (mL)) It was added to a reactor, and the reaction was performed by heating to a temperature of 150 ° C. After the reaction, the reaction mixture was allowed to stand under a vacuum of 100 mTorr for 20 minutes to remove the acetic acid produced by replacing oleic acid with zinc. Thereafter, the reaction mixture was heated to a temperature of 310 ° C to obtain a transparent mixture, and the transparent mixture was maintained at a temperature of 310 ° C for 20 minutes. Then, 0.4 millimolar (mmol) of selenium powder and 2.3 millimolar (mmol) of sulfur powder were dissolved in 3 ml (mL) of trioctylphosphine selenium (Se) and sulfur (S) solution It was quickly injected into a reactor containing a solution of cadmium oleate (Cd (OA) ₂ ) and zinc oleate (Zn (OA) ₂ ). This obtained mixture was grown at a temperature of 310 ° C. for 5 minutes, and then placed in an ice bath to stop the growth. After that, ethanol precipitation was performed. The quantum dots were separated by centrifugation, and excess impurities were washed with chloroform and ethanol. Therefore, a quantum dot particle A composed of particles having a cadmium selenium (core) / zinc sulfide (shell) (CdSe (core) / ZnS (shell)) structure and stabilized by oleic acid was obtained. Specifically, the sum of the core particle diameter and the shell thickness is 3 to 5 nanometers (nm).

Preparation example 2. Synthesis of alkali-soluble resin

A flask prepared with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was prepared. 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 T-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) are added here The flasks were mixed and prepared for a single dropping lot of one monomer. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed, and a drop dispenser for a chain transfer agent was prepared.

Then, 395 parts by weight of PGMEA was poured into the flask, and the atmosphere in the flask was changed from air to nitrogen. During the stirring, the temperature of the flask was raised to 90 ° C. The monomer and the chain transfer agent are then added dropwise using the dropping funnel. Each dropping process was performed for 2 hours while maintaining a temperature of 90 ° C. After 1 hour, the temperature rose to 110 ° C and maintained for 3 hours. Then, a gas inlet tube is used to cause bubbling of a mixed gas (oxygen / nitrogen = 5/95 (volume (v) / volume (v))). Subsequently, 10 parts by weight of glycidyl methacrylate and 0.4 parts by weight of 2,2'-methylenebis (4-methyl-6-tert-butylphenol (2,2'-methylenebis ( 4-methyl-6-t-butylphenol)) and 0.8 parts by weight of triethylamine were added to the flask, and the reaction was continued at a temperature of 110 ° C for 8 hours. Then, the reaction product was cooled to room temperature to obtain A monobasic soluble resin having a solid content of 29.1 weight percent (%), a weight average molecular weight of 32,000, and an acid value of 114 milligrams (mg) of potassium hydroxide (KOH) per gram (g).

Examples and Comparative Examples: Preparation of a self-luminous photosensitive resin composition

The self-luminous photosensitive resin compositions according to Examples and Comparative Examples were prepared based on the compositions and components shown in Tables 1 to 3 below. However, in the case of the self-luminous photosensitive resin composition according to the comparative example, a first metal oxide and a second metal oxide are selected, and the scattering particles according to Table 1 cannot satisfy the scattering particles according to the present invention. . 【Table 1】 【Table 2】 【table 3】

Preparation of color filters

The color filters are prepared using the self-luminous photosensitive resin compositions prepared according to the examples and comparative examples. Each self-luminous photosensitive resin composition is applied on a glass substrate using a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Subsequently, a test photomask having a square-shaped transmittance pattern with a size of 20 millimeters (mm) x 20 millimeters (mm) and a line / space pattern (from 1 to 100 micrometers (µm)) line / space pattern) is placed on the film. The distance between the test mask and the film was set to 100 micrometers (µm), and the test mask was irradiated with ultraviolet light.

At this time, an ultra-high-pressure mercury lamp (product name: USH-250D) manufactured by USHIO DENKI Co., Ltd. was used as an ultraviolet light light source. In air atmosphere, light irradiation (365 nanometers (nm)) is performed with an exposure dose of 200 millijoules / cm ² (mJ / cm ² ), and there is no specific use Filter.

This thin film irradiated with ultraviolet light was immersed in an aqueous potassium hydroxide (KOH) solution having a pH of 10.5 for 80 seconds for development. The glass plate coated with the film was rinsed with distilled water, dried with a nitrogen gas blow, and heated to a temperature of 150 ° C. for 10 minutes in a heating oven to prepare a color filter. Pattern (color filter pattern). The thickness of the prepared color pattern is 5.0 micrometers (µm).

Example 1: Measurement of Fine Pattern

In the color filters prepared using the self-luminous photosensitive resin compositions according to the examples and comparative examples, a line / space mask pattern designed with a 100 micron (µm) size was used. The size of the pattern was measured using OM equipment (ECLIPSE LV100POL, NIKON Co.). The difference between the design value and the measured value of the line / space mask pattern is shown in Table 4 below. 【Table 4】

When the difference between the design value of the line / space mask pattern and the measured value of the obtained fine pattern is 20 micrometers (µm) or more, it may be difficult to achieve a fine pixel. When the difference is a negative value, this is a critical value that causes the process to fail.

Example 2: Measurement of luminous intensity

In the color filters prepared using the self-luminous photosensitive resin compositions according to the examples and comparative examples, a photo-converted area formed in a part of a 20x20 millimeter (mm) square pattern is a photo-converted area. 365 nanometer (nm) tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) was used for measurement. The emission intensity of 450 nanometers (nm) was measured using a spectrometer (Ocean Optics Co.). 【table 5】

The intensity of the measured luminous intensity is directly proportional to the luminous efficiency. Referring to Table 5, the color filters according to Comparative Examples 1 to 10, which cannot meet this demand, include titanium dioxide (as the first metal oxide) having an average particle size of not less than 100 to less than 500 nanometers (nm). ) The color filters according to Examples 1 to 6 with zinc oxide (as a second metal oxide) having an average particle diameter of 30 to 500 nanometers (nm) have excellent brightness.

Example 3: Measurement of reflection brightness

In the color filters prepared using the self-luminous photosensitive resin compositions according to the examples and comparative examples, the reflection brightness by external light is used in a part formed in a 20x20 millimeter (mm) square pattern. An integrating sphere reflectometer (CM-3700D, Konica Minolta). [Table 6]

The fact that the measured low reflection brightness indicates that the visibility due to reflection of external light is excellent. Referring to Tables 4 and 6, compared with oxidation including titanium dioxide (as a first metal oxide) having an average particle diameter of 100 to 500 nanometers (nm) and oxidation having an average particle diameter of 30 to 500 nanometers (nm) The color filters according to Examples 1 to 6 of zinc (as the second metal oxide) cannot meet the requirements of Examples 1 to 6 due to the reflection of external light. The color filters according to Comparative Examples 1 to 10 may not Visibility cannot be satisfied but brightness and fine pattern characteristics can be satisfied.

In other words, it includes titanium dioxide (as the first metal oxide) having an average particle diameter of 100 to 500 nanometers (nm) and zinc oxide (as the second metal) having an average particle diameter of 30 to 500 nanometers (nm). (Oxide) The color filters according to Examples 1 to 6 are excellent in fine pattern characteristics, light emission intensity, and reflection brightness.

When the self-luminous photosensitive resin composition according to the present invention includes specific scattering particles, a decrease in fluorescence efficacy and light retention can be prevented, and a color filter having excellent reflection brightness can be prepared.

In addition, a color filter and an image display device prepared using the self-luminous photosensitive resin composition according to the present invention are self-luminous. Therefore, the color filter and the image display device exhibit excellent color reproducibility and high light retention, and can realize vivid high-quality image quality.

In summary, although the present invention has been disclosed as above with the embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application.

Claims (10)

A self-luminous photosensitive resin composition includes quantum dots and a plurality of scattering particles, wherein the scattering particles include a first metal oxide having an average particle diameter of 100 to 500 nanometers (nm) and 30 to 500 A second metal oxide with an average particle size of nanometers (nm), wherein the first metal oxide is titanium dioxide (TiO ₂ ) and the second metal oxide is zinc oxide (ZnO). The self-luminous photosensitive resin composition according to item 1 of the patent application range, wherein a ratio between an average particle diameter of the second metal oxide and an average particle diameter of the first metal oxide is 0.1 to 0.5. The self-luminous photosensitive resin composition according to item 2 of the scope of the patent application, wherein the difference between the average particle diameter of the first metal oxide and the average particle diameter of the second metal oxide is 60 nanometers (nm ) Or greater than 60 nanometers (nm). The self-luminous photosensitive resin composition according to item 1 of the patent application scope, wherein the scattering particles further include one or more selected from the group consisting of lithium (Li), beryllium (Be), boron (B), and sodium (Na ), Magnesium (Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), thorium (Sc), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe ), Nickel (Ni), copper (Cu), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), molybdenum (Mo), cesium (Cs), barium (Ba ), Lanthanum (La), thorium (Hf), tungsten (W), thorium (Tl), lead (Pb), cerium (Ce), thorium (Pr), neodymium (Nd), thorium (Pm), thorium (Sm ), 铕 (Eu), 釓 (Gd), 鋱 (Tb), 镝 (Dy), “(Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), antimony (Sb), tin (Sn ), Zirconium (Zr), niobium (Nb), cerium (Ce), tantalum (Ta) and indium (In) metal oxides. The self-luminous photosensitive resin composition according to item 4 of the scope of the patent application, further comprising one or more metal oxides selected from the group consisting of aluminum oxide (Al ₂ O ₃ ) and silicon dioxide (SiO ₂ ), Zirconium dioxide (ZrO ₂ ), barium titanate (BaTiO ₃ ), tantalum pentoxide (Ta ₂ O ₅ ), titanium trioxide (Ti ₃ O ₅ ), indium tin oxide (ITO), indium zinc oxide (IZO), arsenic trioxide (ATO), zinc oxide-aluminum (ZnO-Al), niobium trioxide (Nb ₂ O ₃ ), tin oxide (SnO), and magnesium oxide (MgO). The self-luminous photosensitive resin composition according to item 1 of the scope of patent application, wherein 50 to 90 parts by weight of the first metal oxide and 100% by weight of the first solid oxide and 100% by weight of the total solid content of the scattering particles are present. Less than 10 to less than 50 parts by weight of the second metal oxide. The self-luminous photosensitive resin composition according to item 1 of the scope of application for a patent, wherein the self-luminous photosensitive resin composition contains 0.1 to 50 parts by weight of the total solid content relative to 100 parts by weight of the self-luminous photosensitive resin composition. Scattering particles. The self-luminous photosensitive resin composition described in item 1 of the scope of patent application, further comprising one or more selected from the group consisting of photopolymerizable compounds, alkali-soluble resins, and photopolymerization. The type of group consisting of a photopolymerization initiator and a solvent. A color filter including a hardened body of the self-luminous photosensitive resin composition according to any one of claims 1 to 8 of the patent application scope. The color filter includes one or more selected from a red The type of the group consisting of a pattern layer, a green pattern layer, and a blue pattern layer. An image display device includes the color filter described in item 9 of the scope of patent application.