WO2018097464A1 - Spontaneous emission photosensitive resin composition, color filter manufactured using same, and image display apparatus - Google Patents

Abstract

According to the present invention, a spontaneous emission photosensitive resin composition comprises a quantum dot and scattering particles, wherein the scattering particles comprise a first metal oxide having an average particle diameter of 100-500 nm and a second metal oxide having an average particle diameter of 30-500 nm, the first metal oxide is TiO₂, and the second metal oxide is ZnO.

Description

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

The present invention relates to a self-luminous photosensitive resin composition comprising specific scattering particles, a color filter manufactured using the same, and an image display device.

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units. The size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment-dispersible photosensitive resin has been applied, but a part of the light is absorbed by the color filter while the light emitted from the light source passes through the color filter. The problem is that the efficiency is lowered and the color reproduction is lowered due to the characteristics of the pigment contained in the color filter.

In particular, as color filters are used in various fields, including various image display devices, not only excellent pattern characteristics but also high color reproducibility and excellent performance such as high brightness and high contrast ratio are required. A color filter manufacturing method using a self-luminous photosensitive resin composition is proposed.

But quantum dots are essentially non-scattering particles because of their nanoscale size. Therefore, when the light passes through the color filter containing the quantum dot has a much shorter optical path than in the case of other dyes or pigments, most of the light is absorbed by the quantum dot unless the thickness of the color filter is sufficient. In this regard, a method of introducing scattering particles has been proposed, but a situation in which light efficiency is lowered due to light absorption due to scattering particles occurs.

Republic of Korea Patent Publication No. 10-2012-0131071 relates to an optical member and a display device including the same, a host layer; A plurality of wavelength converting particles disposed in the host layer; And an optical member including a plurality of inorganic particles disposed in the host layer, but there is a problem that it is difficult to expect an effect of improving luminous efficiency.

Korean Patent Laid-Open Publication No. 10-2010-0037283 relates to a liquid crystal display device and a manufacturing method thereof, and discloses a liquid crystal display device including a transparent light diffusion layer made of a transparent polymer including a plurality of transparent beads. Since the size of the transparent beads is very large, there is a problem that can bring down the quality of the coating film.

Therefore, there is a demand for development of scattering particles that can be applied to high reliability panels by improving luminous efficiency and light retention.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Republic of Korea Patent Publication No. 2012-0131071 (2012.12.04.)

(Patent Document 2) Republic of Korea Patent Publication No. 2010-0037283 (2010.04.09.)

An object of this invention is to provide the self-luminous photosensitive resin composition which shows the outstanding color reproducibility and can ensure high light retention property.

In addition, the present invention is to provide a color filter and an image display device excellent in luminous efficiency, light retention or reflectance produced using the above self-luminous photosensitive resin composition.

Self-luminous photosensitive resin composition according to the present invention for achieving the above object is a quantum dot; And scattering particles, wherein the scattering particles include a first metal oxide having an average particle diameter of 100 nm to 500 nm; And a second metal oxide having an average particle diameter of 30 nm to 500 nm. The first metal oxide is TiO ₂ , and the second metal oxide is ZnO.

Moreover, this invention provides the color filter containing the hardened | cured material of the above self-luminous photosensitive resin composition.

In addition, the present invention provides an image display device including the color filter described above.

The self-luminous photosensitive resin composition according to the present invention has the advantage of being able to suppress the decrease in the fluorescence luminous efficiency and the light retention rate by including the specific scattering particles, and to produce a color filter having excellent reflectance.

In addition, since the color filter and the image display device made of the self-luminous photosensitive resin composition according to the present invention are capable of self-luminous, not only do they exhibit excellent color reproduction, but also have high light retention and high vivid image quality. have.

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

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

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

<Self-luminous photosensitive resin composition>

One aspect of the invention, quantum dots; And scattering particles, wherein the scattering particles include a first metal oxide having an average particle diameter of 100 nm to 500 nm; And a second metal oxide having an average particle diameter of 30 nm to 500 nm, wherein the first metal oxide is TiO ₂ , and the second metal oxide is ZnO.

Quantum dots

The quantum dots included in the self-luminous photosensitive resin composition of the present invention are nano-sized semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are characteristic of semiconductors. These quantum dots have the characteristic of emitting energy corresponding to the energy band gap when they reach the excited state from the outside. In short, the self-luminous photosensitive resin composition of this invention can self-luminous by including such a quantum dot.

In a typical image display apparatus including a color filter, white light is transmitted through the color filter to implement color. In this process, a part of the light is absorbed by the color filter, thereby degrading light efficiency. However, in the case of including the color filter made of the self-luminous photosensitive resin composition according to the present invention, since the color filter is self-luminous by the light of the light source, it is possible to implement more excellent light efficiency, and also emit light with color Since the color reproducibility is excellent, and the light is emitted in all directions by the photoluminescence, the viewing angle is also improved.

The quantum dots are not particularly limited as long as they can emit light by stimulation by light, and examples thereof include Group II-VI semiconductor compounds, Group III-V semiconductor compounds, Group IV-VI semiconductor compounds, and Group IV elements or compounds containing the same. One or more types selected from can be used.

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

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

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

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

The quantum dots are homogeneous single structures; Dual structures such as core-shell structures, gradient structures, and the like; Or a mixed structure thereof. For example, in the dual structure of the core-shell, the material forming each core and shell may be made of the above-mentioned different semiconductor compounds. More specifically, the core may include one or more materials selected from CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more materials selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

As the colored photosensitive resin composition used in manufacturing a conventional color filter includes colorants of red, green, and blue for color implementation, photoluminescence quantum dots may also 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 emitting red light, green quantum dots emitting green light, or blue quantum dots emitting blue light.

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

The wet chemical process is a method of growing a particle by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Therefore, the nano solvent is easier and cheaper than the vapor deposition method such as the organometallic chemical vapor deposition process or molecular beam epitaxy. Since the growth of the particles can be controlled, it is preferred to produce the quantum dots according to the invention using the wet chemical process.

The content of the quantum dot is not particularly limited in the present invention, but is preferably included 3 to 80 parts by weight, preferably 5 to 70 parts by weight based on 100 parts by weight of the total solids of the self-luminous photosensitive resin composition. When the quantum dots are included in the above range, the light emitting efficiency is excellent and the pixel pattern may be easily formed. When the quantum dots are included in the range below the luminous efficiency may be insufficient, and when the quantum dots exceed the range, it is preferable to satisfy the above range because the formation of the pixel pattern may be somewhat difficult due to the insufficient content of other components. .

Scattering particles

Scattering particles according to the present invention are used to increase the light efficiency of the color filter. While not wishing to be bound by theory, in general, light irradiated from a light source is incident on the color filter at a critical angle, and the spontaneous emission light emitted by the incident light or quantum dots by itself meets the scattering particles and increases the light path. As a result, the light emission intensity is increased, and as a result, the light efficiency of the color filter can be increased.

Scattering particles according to the invention the first metal oxide having an average particle diameter of 100nm to 500nm; And a second metal oxide having an average particle diameter of 30 nm to 500 nm. The first metal oxide is TiO ₂ , and the second metal oxide is ZnO.

In the present invention, the "average particle diameter" may be a number average particle diameter, and can be obtained from an image observed by, for example, a field emission runner electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples can be extracted from the observed images of FE-SEM or TEM, and the diameters of these samples can be measured to obtain arithmetic mean values.

The scattering particles according to the present invention 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, and include TiO ₂ as the first metal oxide, wherein the second metal By including ZnO as an oxide, it is possible to manufacture a color filter not only having excellent light emission intensity but also excellent reflection brightness.

When the first metal oxide is included in the self-luminous photosensitive resin composition, there is an advantage that it is possible to sufficiently sustain the light emission by playing a role of increasing the emission retention rate. In addition, when the second metal oxide having an average particle diameter of 30 to 500 nm is included in the self-luminous photosensitive resin composition, the light path may be increased by inducing sufficient scattering of light, thereby improving the light emission intensity. In addition, it is possible to manufacture a color filter having high luminance and light retention.

If the average particle diameter of the scattering particles is less than the above range, for example, 10 nm, the scattering effect of the incident light or the light emitted from the quantum dots cannot be expected. If the scattering particles become too large beyond the above range, the particles sink in the composition and have a uniform quality. There is a problem that the surface of the light emitting layer cannot be obtained.

Therefore, in the present invention, as the scattering particles, 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 are used together, and the first metal oxide includes TiO ₂ , and the second metal Since the oxide contains ZnO, not only excellent light emission characteristics but also effective prevention of oxidation of quantum dots generated during a post bake (PB) process may reduce the luminance decrease occurring between processes.

In one embodiment of the present invention, the ratio of the average particle diameter of the first metal oxide and the second metal oxide may be 0.1 to 0.5 times. Specifically, it is preferable to use a first metal oxide having an average particle diameter of 100 to 500 nm, preferably 150 to 400 nm as scattering particles, wherein the average particle diameter of the second metal oxide is an average particle diameter of the first metal oxide. It is preferable to use 0.1 to 0.5 times as much.

In another embodiment of the present invention, the average particle diameter of the second metal oxide is not larger than the particle diameter of the first metal oxide, and in this case, since uniform mixing is possible, a surface of the self-luminous layer of uniform quality can be obtained. There is an advantage. Specifically, in another embodiment of the present invention, the difference in average particle diameter of the first metal oxide and the second metal oxide may be 60 nm or more.

In another embodiment of the present invention, the scattering particles are Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sb, It may further include an oxide of at least one metal selected from Sn, Zr, Nb, Ce, Ta and In.

In another embodiment of the present invention, the metal oxide further included is Al ₂ O ₃ , SiO ₂ , ZrO ₂ , BaTiO ₃ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al , Nb ₂ O ₃ , SnO and may be one or more selected from MgO, and if necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

In another embodiment of the present invention, it may be included in less than 50 to 90 parts by weight of the first metal oxide and less than 10 to 50 parts by weight of the second metal oxide with respect to 100 parts by weight of the total scattering particle solids. When the first metal oxide and the second metal oxide satisfy the above range, it is preferable because the effect of improving the light retention rate is excellent and the reduction of the luminance can be suppressed. When the first metal oxide is less than the above range, the effect of improving the light retention rate may be insignificant, and when the first metal oxide exceeds the above range, the luminance may decrease as the scattering effect decreases. When the content of the second metal oxide is less than the above range, light scattering is difficult, and thus the luminance improvement effect may be insignificant. If the content of the second metal oxide exceeds the above range, there is a possibility that it may hinder the improvement of the light retention rate.

The scattering particles may be limited in content in the entire composition to sufficiently improve the light emission intensity of the color filter. Specifically, in another embodiment of the present invention, the scattering particles may be included in 0.1 to 50 parts by weight, preferably 0.3 to 30 parts by weight based on 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. When the scattering particles are included in the above range, there is an advantage in that a color filter having excellent emission intensity and stable performance thereof may be manufactured. When the scattering particles are included in less than the above range it may be difficult to secure the desired luminescence intensity, when the scattering particles are exceeded the range of the self-luminous photosensitive resin composition containing the scattering particles as well as the effect of increasing the luminescence intensity is insufficient Since stability may fall, it is preferable to use within the said range.

In another embodiment of the present invention, the self-luminous photosensitive resin composition may further include one or more selected from the group consisting of a photopolymerizable compound, an alkali-soluble resin, a photopolymerization initiator and a solvent.

Photopolymerizable  compound

The self-luminous photosensitive resin composition according to the present invention may include a photopolymerizable compound. The photopolymerizable compound may be a monofunctional monomer, a bifunctional monomer or a trifunctional or higher polyfunctional monomer as a compound which can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator described later.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpi Commercially available products include, but are not limited to, Aronix M-101 (Doagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscot 158 (Osaka Yuki Kagaku High School), but are not limited thereto. It is not.

Specific examples of the bifunctional monomers include 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethylene glycoldi (meth) acrylate, neopentylglycoldi (meth) acrylic The rate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned, As a commercial item, Aronix M-210 is mentioned. , M-1100, 1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Biscotti 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa), etc. It may include, but is not limited thereto.

Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and penta. Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated Dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; commercially available aronix M-309 , TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nipbon Kayaku), but are not limited thereto. .

In addition, the photopolymerizable compound may include dipentaerythritol (poly) acrylate having a hydroxyl group or a carboxylic acid group as in the following Chemical Formulas 1 to 2, and the like.

In Formula 1, R ₁ is an acrylate group or methacrylate group, R ₂ is hydrogen, acryloyl group or methacryloyl group.

In Formula 2, R ₃ to R ₅ are the same as or different from each other, and each is OH, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group, or -OR ₇ . At this time, at least one of R ₃ to R ₅ is an acrylate group or methacrylate group, R ₇ is

to be. R ₆ is —C (═O) CH ₂ CH ₂ C (═O) OH, R ₈ and R ₉ are acrylate or methacrylate groups, and R ₁₀ is hydrogen, acryloyl group, methacryloyl group Or -C (= 0) CH ₂ CH ₂ C (= 0) OH.

As the photopolymerizable compound of the present invention, a bifunctional or more than one polyfunctional monomer can be preferably used, and more preferably, a carboxylic acid group-containing 5-functional photopolymerizable compound can be used. In the case of using a polyfunctional monomer having five or more functional groups, the formation of the pixel pattern is more excellent and preferable. In particular, the 5-functional or higher polyfunctional monomer containing a carboxylic acid group can form a pixel pattern having excellent light reactivity and excellent light reactivity without deterioration in luminescence properties due to particle aggregation of the quantum dots.

The photopolymerizable compound may be included in an amount of 5 to 70 parts by weight, preferably 7 to 65 parts by weight, based on 100 parts by weight of the total solids of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included below the above range, the intensity or smoothness of the pixel portion becomes good, which is preferable. When the photopolymerizable compound is included below the range, the degree of photocuring by light may be lowered, and thus, the formation of the pixel pattern may be somewhat difficult. When the photopolymerizable compound is exceeded, the problem of pattern separation may occur.

Alkali soluble resin

The self-luminous photosensitive resin composition of this invention can contain alkali-soluble resin. The said alkali-soluble resin is a component which provides solubility with respect to the alkaline developing solution used at a image development process. In short, the alkali-soluble resin may play a role of making the non-exposed portion of the photosensitive resin layer alkali-soluble using the self-luminous photosensitive resin composition, and in the present invention, any resin that is soluble in an alkaline developer may be used without particular limitation. This is possible.

Specifically, the alkali-soluble resin may be prepared by copolymerizing at least one selected from an unsaturated monomer having a carboxyl group and a monomer having an unsaturated bond copolymerizable therewith, but is not limited thereto.

Unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated polycarboxylic acid, etc. can be used as an unsaturated monomer which has the said carboxyl group.

Specifically, as said unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As said unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of both terminal dicarboxy polymers, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. The unsaturated monomer which has these carboxyl groups can be used individually or in mixture of 2 or more types, respectively.

In addition, the monomer having an unsaturated bond copolymerizable with the unsaturated monomer having a carboxyl group may be an aromatic vinyl compound, an unsaturated carboxylic ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, or carboxyl. Selected from acid vinyl ester compounds, unsaturated ether compounds, vinyl cyanide compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, macromonomers and bulky monomer compounds having a monoacryloyl group or a monomethacryloyl group at the ends of the molecular chain 1 or more types can be used.

More specifically, the monomer having a copolymerizable unsaturated bond is styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) a Relate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic ester compounds of;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl ester compounds;

Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl ester 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;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethyl methacrylamide, maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclo Unsaturated imide compounds such as hexyl maleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Macromonomers having;

Bulky monomers, such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton, which can lower the dielectric constant, can be used.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 200,000, and more preferably in the range of 5,000 to 100,000, in order to improve surface hardness for use as a color filter. Further, the molecular weight distribution, it is preferable (M _w / M _n) is from 1.5 to 6.0, more preferably in the range of 1.8 to 4.0. When the weight average molecular weight and the molecular weight distribution of the alkali-soluble resin are within the above ranges, the hardness is improved, has a high residual film ratio, excellent solubility of the non-exposed portions in the developing solution, and the resolution can be improved.

It is preferable that the acid value of the said alkali-soluble resin is 20-200 mgKOH / g based on solid content. The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the acrylic polymer and is involved in solubility. When the acid value of the resin is within the above range, the solubility in the developer is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development, thereby improving the film remaining ratio.

The alkali-soluble resin may be included in a weight fraction of preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight based on 100 parts by weight of the total solids in the self-luminous photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in the developing solution is sufficient, so that the non-pixel portion is easily missing, so that residues do not easily occur on the substrate, and the film portion of the exposed portion of the exposed portion is prevented during development. It is preferable because it becomes easy to form a pattern. If the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.

Photopolymerization Initiator

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention generates radicals and the like capable of initiating polymerization of the photopolymerizable compound described above by exposure to radiation such as visible light, ultraviolet light, ultraviolet rays, electron beams, and X-rays. It is a compound.

The photopolymerization initiator may be applied to those commonly used in the art within the scope of not impairing the object of the present invention, and the kind is not particularly limited as long as it can polymerize the binder resin and the photopolymerizable compound. Representative examples include, but are not limited to, triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, and oxime-based compounds, and one or more kinds thereof may be selected and used therefrom.

Since the self-luminous photosensitive resin composition containing the said photoinitiator becomes highly sensitive and the pixel part of the pixel pixel of the color filter formed from the said self-luminous photosensitive resin composition becomes favorable in intensity or pattern property, it is preferable to include the said photoinitiator. .

Specifically, as the triazine-based compound, 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-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -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- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like, but is not limited thereto.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned. Moreover, the compound represented by following formula (3) is mentioned.

In Formula 3, R ₁ to R ₄ are each independently hydrogen, halogen, OH, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or It is a naphthyl group unsubstituted or substituted by a C1-C12 alkyl group.

As a compound represented by the said Formula (3), for example, 2-methyl- 2-amino (4-morpholino phenyl) ethane- 1-one, 2-ethyl- 2-amino (4-morpholino phenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole type compound compound, it is 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-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) And imidazole compounds in which the phenyl group at the -4,4'5,5'-tetraphenyl-1,2'-biimidazole or 4,4 ', 5,5' position is substituted with a carboalkoxy group. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-are more preferable. 4,4 ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole Etc. can be used.

As said oxime type compound, o-ethoxycarbonyl- (alpha)-oxyimino- 1-phenyl propane- 1-one, for example, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -ethanone-1- (O-acetyloxime), (Z) -2-((benzoyloxy) imino) -1- (4- (phenylthio) phenyl) octan-1-one, (E) -1-(((1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) ethylidin) amino) oxy) ethanone and (E) -1- (((1- (6- (4-((2,2-dimethyl-1,3-dioxolan-4-yl) methoxy) -2-methylbenzoyl) -9-ethyl-9H-carbazole-3 -Yl) ethylidine) amino) oxy) ethanone, and the like, but commercially available products include BASF's OXE-01 and OXE-02, but are not limited thereto. In addition, the following Chemical Formulas 4 to 6 may be mentioned.

Moreover, it is also possible to further use the other photoinitiator normally used within the range which does not impair the effect of this invention. Specific examples of the other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, other photopolymerization initiators, and the like. These can be used individually or in mixture of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

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

Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, Methyl phenyloxyoxylate, a titanocene compound, etc. are mentioned.

The photopolymerization initiator is preferably contained in a weight fraction of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to the solid content in the self-luminous photosensitive resin composition of the present invention. When the content of the photopolymerization initiator is in the above-described range, the self-luminous photosensitive resin composition is highly sensitive, so that the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Moreover, since the intensity | strength and smoothness in the surface of the said pixel part formed using the self-luminous photosensitive resin composition of this invention can become favorable, it is preferable.

On the other hand, in order to improve the sensitivity of the self-luminous photosensitive resin composition of this invention, the said photoinitiator can be used together with a photoinitiator. When the self-luminous photosensitive resin composition of this invention contains a photoinitiation start adjuvant, since a sensitivity becomes high and productivity at the time of forming a color filter using this composition is preferable, it is preferable.

The photopolymerization initiation adjuvant may be preferably used one or more compounds selected from, for example, amine compounds and carboxylic acid compounds.

As said amine compound, For example, aliphatic amine compounds, such as triethanolamine, methyl diethanolamine, and triisopropanolamine, 4-dimethylamino benzoate methyl, 4-dimethylamino benzoate ethyl, 4-dimethylamino benzoate isoamyl, 4- Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis ( Diethylamino) benzophenone and the like. As the amine compound, it may be preferable to use an aromatic amine compound.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid and chlorophenylthioacetic acid. And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiation adjuvant is preferably included in a weight fraction of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to the solid content in the self-luminous photosensitive resin composition. When the content of the photopolymerization initiation aid is within the above-mentioned range, the sensitivity efficiency of the self-luminous photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition tends to be improved, which is preferable.

solvent

The solvent included in the self-luminous photosensitive resin composition according to the present invention can be used without particular limitation as long as it is effective in dissolving other components included in the self-luminous photosensitive resin composition. The solvent may include, for example, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters, but may be selected from one or more thereof, but is not limited thereto.

Specific examples of the ether solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Etc. can be mentioned.

Specific examples of the acetate solvents include ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; Etc. can be mentioned.

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

Specific examples of the ketone solvents include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specific examples of the alcohol solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.

Specific examples of the ester solvents include esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; Etc. can be mentioned.

The solvents may be used alone or in combination of two or more thereof.

Among the solvents, organic solvents having a boiling point of 100 to 200 ° C. in terms of coatability and dryness are preferable, and alkylene glycol alkyl ether acetates are more preferable; Ketones; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Etc. can be mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

In the present invention, the content of the solvent is not particularly limited, and may include 60 to 90 parts by weight of the solvent, and more preferably 60 to 85 parts by weight, based on 100 parts by weight of the total amount of the self-luminous photosensitive resin composition. . When the content of the solvent is within the above-mentioned range, the coating property is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. Can be provided. When the content of the solvent is less than the above range, the process may be somewhat difficult as the applicability is slightly lowered. If the solvent content exceeds the above range, the performance of the color filter formed of the self-luminous photosensitive resin composition may be slightly lowered. Problems may arise.

additive

The self-luminous photosensitive resin composition according to the present invention may further include additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like as necessary.

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

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively.

As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl peer ether, polyethyleneglycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

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

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

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

<Color filter>

Another aspect of the present invention relates to a color filter made of the above-described self-luminous photosensitive resin composition.

When the color filter according to the present invention is applied to an image display device, the color filter emits light by the light of the display device light source, and thus it is possible to realize more excellent light efficiency. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, thereby improving the viewing angle.

Specifically, the color filter according to the present invention includes a first metal oxide having an average particle diameter of 100 nm to 500 nm and a second metal oxide having an average particle diameter of 30 nm to 500 nm, wherein the first metal oxide is TiO ₂ , and the second metal oxide. Since ZnO contains hardened | cured material of the self-luminous photosensitive resin composition, it has the advantage of being excellent in light retention and excellent in reflectance.

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

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer including the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern.

The pattern layer formed of 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 pattern layer containing blue quantum dot particles. When the light is irradiated, the red pattern layer may emit red light, the green pattern layer may emit green light, and the blue pattern layer may emit blue light. In such a case, the emission light of the light source is not particularly limited when applied to an image display device to be described later, but it is preferable to use a light source that emits blue light in view of better color reproducibility.

In another embodiment of the present invention, the pattern layer may include one or more 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 a pattern layer having two colors of a red pattern layer, a green pattern layer, and a blue pattern layer, and in this case, the pattern layer may further include a transparent pattern layer containing no quantum dot particles.

When only the pattern layer of the two colors is provided, a light source that emits light having a wavelength representing the remaining colors 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 such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light as it is transmitted.

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

<Image display device>

Another aspect of the present invention relates to an image display apparatus including the above-described color filter. The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, and field emission display devices as well as ordinary liquid crystal display devices.

The image display device according to the present invention has an advantage of excellent light efficiency, high luminance, excellent color reproducibility, excellent reflection luminance, and a wide viewing angle.

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

Production Example  One. CdSe (core)/ ZnS Synthesis of Photoluminescent Green Quantum Dot Particle A with (Shell) Structure

CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 mL) were added to the reactor together with 1-octadecene (20 mL) and heated to 150 ° C. Reacted. Thereafter, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr to remove acetic acid produced by substitution of oleic acid with zinc. Then, 310 ° C. heat was applied to obtain a clear mixture. After maintaining 310 ° C. for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. And S solution was rapidly injected into the reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C. for 5 minutes and then stopped using an ice bath. Then, precipitated with ethanol to separate the quantum dots using a centrifuge and the excess impurities washed with chloroform and ethanol, stabilized with oleic acid, the core particle diameter and the sum of the shell thickness of 3 to 5nm A quantum dot particle A having a CdSe (core) / ZnS (shell) structure in which they were distributed was obtained.

Production Example  2. Synthesis of Alkali Soluble Resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were added and stirred and mixed to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanediol. 24 parts by weight of PGMEA was added thereto, followed by stirring and mixing to prepare a dropping chain for a chain transfer agent.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition proceeds for 2 hours each while maintaining 90 ° C, and after 1 hour, the temperature is raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube is introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. The ring started. Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask, followed by 8 hours at 110 ° C. The reaction was continued and an alkali-soluble resin having a solid content of 29.1 wt%, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g was then cooled to room temperature.

Example  And Comparative example  : Self-luminescence  Preparation of Photosensitive Resin Composition

To the composition and the content according to Tables 1 to 3 to prepare a self-luminous photosensitive resin composition according to Examples and Comparative Examples. However, at this time, the self-luminous photosensitive resin composition according to the comparative example selected the first metal oxide and the second metal oxide so that the scattering particles according to Table 1 does not satisfy the scattering particles according to the present invention.

	Kinds	Average particle diameter	product name	manufacturer
E-1	TiO 2	70 nm	TTO-51A	Ishihara
E-2	TiO 2	130 nm	PT-401L	Ishihara
E-3	TiO 2	280 nm	CR-95	Huntsmansa
E-4	TiO 2	500 nm	R-960	Dupont
E-5	TiO 2	900 nm	R-902	Dupont
E-6	ZnO	50 nm	721077	Sigma Aldrich
E-7	ZnO	500 nm	Micropowder	US Nano
E-8	ZnO	1000 nm	Micropowder	US Nano

Composition (wt%)		Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6	Comparative Example 7	Comparative Example 8	Comparative Example 9	Comparative Example 10
Quantum Dot A 1)		12	12	12	12	12	12	12	12	12	12
Photopolymerizable compound 2)		10	10	10	10	10	10	10	10	10	10
Photopolymerization initiator 3)		2	2	2	2	2	2	2	2	2	2
Alkali-soluble resin 4)		12	12	12	12	12	12	12	12	12	12
Scattering particles 5)	E-1	4	-	-	-	-	-	-	-	2.8	-
	E-2	-	4	-	-	-	-	-	-	-	-
	E-3	-	-	4	-	-	-	-	-	-	2.8
	E-4	-	-	-	4	-	-	-	-	-	-
	E-5	-	-	-	-	4	-	-	-	-	-
	E-6	-	-	-	-	-	4		-	-	-
	E-7	-	-	-	-	-	-	4	-	1.2	-
	E-8	-	-	-	-	-	-	-	4	-	1.2
Solvent 6 )		60	60	60	60	60	60	60	60	60	60
1) Quantum dot A: CdSe (core) / ZnS (shell) structure of Preparation Example 1 Quantum dot A2) Photopolymerizable compound: Dipentaerythritol pentaacrylate pumpkin acid monoester (carboxylic acid-containing 5-functional photopolymerizable compound) (TO-1382, 3) Photopolymerization initiator: Irgacure-907 (manufactured by BASF) 4) Alkali-soluble resin: Alkali-soluble resin of Preparation Example 5) Scattering particles: Scattering particles according to Table 1 6) Solvent: Propylene glycol monomethyl ether acetate

Composition (wt%)		Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
Quantum Dot A 1)		12	12	12	12	12	12
Photopolymerizable compound 2 )		10	10	10	10	10	10
Photopolymerization initiator 3 )		2	2	2	2	2	2
Alkali-soluble resins 4 )		12	12	12	12	12	12
Scattering Particles 5 )	E-2	2.8	3.6	-	-	-	-
	E-3	-	-	2.8	3.6	-	-
	E-4	-	-	-	-	2.8	3.6
	E-6	1.2	-	1.2	-	1.2	-
	E-7	-	0.4	-	0.4	-	0.4
Solvent 6 )		60	60	60	60	60	60
1) Quantum dot A: CdSe (core) / ZnS (shell) structure of Preparation Example 1 Quantum dot A2) Photopolymerizable compound: Dipentaerythritol pentaacrylate pumpkin acid monoester (carboxylic acid-containing 5-functional photopolymerizable compound) (TO-1382, 3) Photopolymerization initiator: Irgacure-907 (manufactured by BASF) 4) Alkali-soluble resin: Alkali-soluble resin of Preparation Example 5) Scattering particles: Scattering particles according to Table 1 6) Solvent: Propylene glycol monomethyl ether acetate

Manufacture of color filter

The color filter was manufactured using the self-luminous photosensitive resin composition prepared according to the above Examples and Comparative Examples. Each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Subsequently, a test photomask having a transmissive pattern of horizontal × vertical 20 mm × 20 mm squares and a line / space pattern of 1 to 100 μm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm ² under an atmospheric atmosphere using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

The thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern. The film thickness of the color pattern prepared above was 5.0 μm.

Experimental Example  1: fine pattern measurement

The size of the pattern obtained through the line / space pattern mask designed to 100 μm among the color filters manufactured using the self-luminous photosensitive resin composition prepared according to the Examples and Comparative Examples was measured by the OM device (ECLIPSE LV100POL Nikon). Was measured, and the difference from the design value of the line / space pattern mask is shown in Table 4 below.

	Difference in Fine Pattern
Example 1	10
Example 2	11
Example 3	9
Example 4	10
Example 5	8
Example 6	6
Comparative Example 1	9
Comparative Example 2	10
Comparative Example 3	9
Comparative Example 4	7
Comparative Example 5	One
Comparative Example 6	10
Comparative Example 7	8
Comparative Example 8	4
Comparative Example 9	7
Comparative Example 10	One

When the difference between the design value of the line / space pattern mask and the measured value of the obtained fine pattern is 20 µm or more, it is difficult to implement the fine pixel, and a negative value means a threshold value that causes a process defect.

Experimental Example  2: luminous intensity measurement

Part of a color filter manufactured using a self-luminous photosensitive resin composition prepared according to Examples and Comparative Examples was formed through a pattern of 20 × 20 mm square through a 365 nm tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT). The light-converted region was measured, and the emission intensity in the 450 nm region was measured using a Spectrum meter (Ocean Optics).

	Luminous intensity
Example 1	28500
Example 2	34800
Example 3	30800
Example 4	28800
Example 5	34200
Example 6	31300
Comparative Example 1	15200
Comparative Example 2	17700
Comparative Example 3	27500
Comparative Example 4	22500
Comparative Example 5	15300
Comparative Example 6	11300
Comparative Example 7	14700
Comparative Example 8	10100
Comparative Example 9	15700
Comparative Example 10	12800

The higher the measured light emission intensity, the higher the light efficiency. In Table 5, Examples 1 to 6 including TiO ₂ having an average particle diameter of less than 100 nm to 500 nm as the first metal oxide and ZnO having an average particle diameter of 30 nm to 500 nm or less as the second metal oxide, Comparative Examples 1 to 6, which do not satisfy this, It can be seen that the emission luminance is superior to that of 10.

Experimental Example  3: Reflective luminance measurement

Integrating sphere reflectance measuring instrument (CM-3700D, Konika) reflects the luminance of reflection by external light in a portion formed in a 20 × 20 mm square pattern among color filters manufactured using the self-luminous photosensitive resin compositions prepared according to Examples and Comparative Examples. Minolta).

	Reflection
Example 1	17.4
Example 2	16.3
Example 3	19.4
Example 4	20.1
Example 5	19.8
Example 6	21.4
Comparative Example 1	13.8
Comparative Example 2	25.7
Comparative Example 3	31.2
Comparative Example 4	43.4
Comparative Example 5	50.7
Comparative Example 6	4.5
Comparative Example 7	15.3
Comparative Example 8	19.6
Comparative Example 9	12.7
Comparative Example 10	32.3

The lower the measured luminance of reflection, the better the visibility by external light reflection. In Tables 4 and 6, when the first metal oxide does not satisfy Examples 1 to 6 including TiO ₂ having an average particle diameter of less than 100 nm to 500 nm and ZnO having an average particle diameter of 30 nm to 500 nm or less, It can be seen that it is difficult to satisfy the visibility due to external light reflection while satisfying the fine pattern characteristics.

That is, Examples 1 to 6, which include TiO ₂ having an average particle diameter of less than 100 nm to 500 nm as a first metal oxide and ZnO having an average particle diameter of 30 nm to 500 nm or less as a second metal oxide, are excellent in all of fine pattern measurement, emission intensity measurement, and reflection luminance. It can be seen that.

Claims (11)

1. Quantum dots; And

   Including scattering particles,

   The scattering particles are a first metal oxide having an average particle diameter of 100nm to 500nm; And a second metal oxide having an average particle diameter of 30 nm to 500 nm.

   The first metal oxide is TiO ₂ ,

   The second metal oxide is ZnO self-luminous photosensitive resin composition.
2. The method of claim 1,

   The ratio of the average particle diameter of the first metal oxide and the second metal oxide is 0.1 to 0.5 times the self-luminous photosensitive resin composition.
3. The method of claim 2,

   The difference in average particle diameter of the first metal oxide and the second metal oxide is 60nm or more self-luminous photosensitive resin composition.
4. The method of claim 1,

   The scattering particles are Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sb, Sn, Zr, Nb, Ce, Ta and A self-luminous photosensitive resin composition further comprising an oxide of at least one metal selected from In.
5. The method of claim 4, wherein

   The additionally included metal oxides are Al ₂ O ₃ , SiO ₂ , ZrO ₂ , BaTiO ₃ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO and MgO A self-luminous photosensitive resin composition which is at least 1 sort (s) chosen from.
6. The method of claim 1,

   Self-luminous photosensitive resin composition comprising less than 50 to 90 parts by weight of the first metal oxide and less than 10 to 50 parts by weight of the second metal oxide with respect to 100 parts by weight of the total scattering particle solids.
7. The method of claim 1,

   The scattering particles are self-luminous photosensitive resin composition which is contained in 0.1 to 50 parts by weight based on 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition.
8. The method of claim 1,

   The self-luminous photosensitive resin composition which further contains 1 or more selected from the group which consists of a photopolymerizable compound, alkali-soluble resin, a photoinitiator, and a solvent.
9. The color filter containing the hardened | cured material of the self-luminous photosensitive resin composition of any one of Claims 1-8.
10. The method of claim 9,

    The color filter is a color filter comprising one or more selected from the group consisting of a red pattern layer, a green pattern layer and a blue pattern layer.
11. An image display apparatus comprising the color filter according to claim 9.