JP2019536110A - Self-luminous photosensitive resin composition, color filter produced using the same, and image display device - Google Patents

Abstract

The self-luminous photosensitive resin composition according to the present invention includes quantum dots; and scattering particles; wherein the scattering particles are a first metal oxide having an average particle size of 100 nm to 500 nm; and an average particle size of 30 nm to 500 nm. Wherein the first metal oxide is TiO2 and the second metal oxide is ZnO. [Selection diagram] None

Description

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

  A color filter is a thin-film optical component that extracts three colors of red, green, and blue from white light and enables them in fine pixel units. Each pixel has a size of several tens to several hundreds of micrometers. Degree. Such a color filter has a black matrix layer formed in a predetermined pattern on a transparent substrate and a plurality of colors (usually a plurality of colors to form each pixel) in order to shield a boundary portion between each pixel. , Red (R), green (G), and blue (B)) are arranged in order of pixel portions arranged in a predetermined order.

  Recently, a pigment dispersion method using a pigment-dispersed photosensitive resin has been applied as one of the methods for embodying a color filter. However, the light emitted from the light source passes through the color filter and passes through the color filter. A part of the light is absorbed by the color filter, resulting in a decrease in light efficiency and a problem that color reproduction is deteriorated due to 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 performance such as excellent high brightness and high contrast ratio are required. However, in order to solve such problems, a method for producing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.

  However, quantum dots are essentially non-scattering particles due to their nano-level size. Therefore, when light passes through a color filter containing quantum dots, it will have a much shorter optical path than other dyes and pigments, and if the color filter is not thick enough, Light is absorbed by the quantum dots. As a result, a method of introducing scattering particles has been proposed, but the problem is that the light efficiency is lowered due to the light absorption phenomenon due to the scattering particles.

  Patent Document 1 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 including a plurality of inorganic particles disposed in the host layer. Although the contents regarding the members are disclosed, there is a problem that it is difficult to expect the effect of improving the luminous efficiency.

  Patent Document 2 relates to a liquid crystal display device and a method for manufacturing the same, and discloses contents related to a liquid crystal display device including a transparent light diffusion layer made of a transparent polymer including a plurality of transparent beads. Since it is very large, there exists a problem which can bring about the fall of coating-film quality.

  Therefore, there is a demand for the development of scattering particles that can be applied to highly reliable panels with improved luminous efficiency and light retention.

Korean Patent Publication No. 2012-0131071 (2012.12.04.) Korean Patent Publication No. 2010-0037283 (2011.04.09)

  An object of this invention is to provide the self-light-emitting photosensitive resin composition which shows the outstanding color reproduction rate and can ensure a high light maintenance factor characteristic.

  In addition, the present invention provides a color filter and an image display device that are manufactured using the above-described self-light-emitting photosensitive resin composition and that are excellent in luminous efficiency, light maintenance rate, or reflection luminance.

The self-luminous photosensitive resin composition according to the present invention for achieving the above object comprises quantum dots; and scattering particles, wherein the scattering particles have a first metal oxide having an average particle size of 100 nm to 500 nm; and A second metal oxide having an average particle size of 30 nm to 500 nm, wherein 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 self-light-emitting photosensitive resin composition mentioned above.

  The present invention also provides an image display device including the color filter described above.

  By including specific scattering particles, the self-luminous photosensitive resin composition according to the present invention can suppress a decrease in fluorescence emission efficiency and light retention rate, and can produce a color filter excellent in reflection luminance. There is an advantage.

  In addition, since the color filter and the image display device manufactured with the self-light-emitting photosensitive resin composition according to the present invention can emit light, the color filter and the image display device have excellent color reproduction ratio, high light maintenance rate, and high quality. There is an advantage that vivid image quality can be realized.

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

  In the present invention, when an arbitrary member is located "on" another member, this is not only when the arbitrary member is in contact with the other member, but also between the two members. Including the case where exists.

  In the present invention, when any part “comprises” a certain component, this does not exclude other components and can further include other components unless otherwise stated. Means.

<Self-light-emitting photosensitive resin composition>
One aspect of the present invention includes: a quantum dot; and a scattering particle, wherein the scattering particle is a first metal oxide having an average particle size of 100 nm to 500 nm; and a second metal having an average particle size of 30 nm to 500 nm An oxide; wherein the first metal oxide is TiO ₂ and the second metal oxide is ZnO.

Quantum dot The quantum dot contained in the self-light-emitting photosensitive resin composition of the present invention is a nano-sized semiconductor material. Atoms form molecules, and molecules form a cluster of small molecules called clusters to form nanoparticles. When such nanoparticles are particularly semiconductor-like, Is called a quantum dot. Such a quantum dot has a characteristic of emitting energy corresponding to the energy band gap when it is excited by receiving energy from the outside. In short, the self-luminous photosensitive resin composition of the present invention is capable of self-luminance by including such quantum dots.

  In a normal image display device including a color filter, white light is transmitted through the color filter to realize a color. In this process, a part of the light is absorbed by the color filter, so that the light efficiency is lowered. However, when the color filter manufactured with the self-light-emitting photosensitive resin composition according to the present invention is included, the color filter emits light by the light of the light source, so that more excellent light efficiency can be realized. Since light having a hue is emitted, the color reproducibility is further improved, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

  The quantum dots are not particularly limited as long as they can emit light by stimulation with light. For example, II-VI group semiconductor compounds, III-V group semiconductor compounds, IV-VI group semiconductor compounds, and IV group elements or the like One or more selected from compounds containing can be used.

The II-VI group semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS 3dCe, selected from the group consisting of ZnDe, ZnDe, ZnSe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HdZnSe, CdZe , CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. May be one or more selected from the group consisting of elemental compounds,
The III-V semiconductor compound is a two-element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; GaNP, GANAS A ternary compound selected from the group consisting of GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, And it may be one or more selected from the group consisting of classical element compound selected from the group consisting of mixtures,
The IV-VI group semiconductor compound is a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbS Or three or more elements selected from the group consisting of SnPbTe and mixtures thereof; and one or more elements selected from the group consisting of four elements selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe and mixtures thereof Often,
The Group IV element or a compound containing the element is an elemental compound selected from the group consisting of Si, Ge, and a mixture thereof; and a group consisting of a two-element compound selected from the group consisting of SiC, SiGe, and a mixture thereof. Although it may be one or more selected, it is not limited to these.

  The quantum dots may have a homogenous single structure; a double structure such as a core-shell structure, a gradient structure, or the like; or a mixed structure thereof. For example, in the core-shell dual structure, the materials constituting the core and the shell may be composed of the above-mentioned different semiconductor compounds. More specifically, the core may include one or more materials selected from, but not limited to, CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO. is not. The shell may include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

  Similarly to the fact that the colored photosensitive resin composition used in the production of a normal color filter contains red, green, and blue colorants for embodying the hue, the photoluminescence quantum dots are also red quantum dots, It can be classified into 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, or blue quantum dots that emit blue light.

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

  The wet chemical process is a method of growing particles by putting a precursor substance in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal, so that the metal organic chemical vapor deposition process and molecular beam epitaxy It is preferable to manufacture the quantum dots according to the present invention using the wet chemical process because the growth of nanoparticles can be controlled through a process that is easier and less expensive than the vapor deposition method.

  Although the content of the quantum dots is not particularly limited in the present invention, it is included in an amount of 3 to 80 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. Better. When the quantum dots are included in the range, there are advantages that light emission efficiency is excellent and a pixel pattern can be easily formed. When the quantum dots are included below the range, the light emission efficiency may be insufficient, and when the range exceeds the range, the content of other components is relatively insufficient, so that it is somewhat difficult to form a pixel pattern. Therefore, it is preferable to satisfy the above range.

Scattering particles The scattering particles according to the invention are used to increase the light efficiency of the color filter. Although not wishing to be limited by theory, in general, light emitted from a light source is incident on a color filter with a critical angle, but at this time, incident light is spontaneously emitted by itself or by quantum dots. The emitted light meets the scattering particles, and the emission intensity becomes stronger due to the increase of the light path. As a result, the light efficiency of the color filter can be increased.

The scattering particles according to the present invention include: a first metal oxide having an average particle size of 100 nm to 500 nm; and a second metal oxide having an average particle size of 30 nm to 500 nm. 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 determined from, for example, a phase observed with a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples can be extracted from the observation image of FE-SEM or TEM, and the diameter of these samples can be measured and obtained as an arithmetic average value.

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 includes TiO ₂ as the first metal oxide. By including ZnO as the second metal oxide, it is possible to produce a color filter having excellent emission intensity and excellent reflection luminance.

  When the first metal oxide is contained in the self-luminous photosensitive resin composition, there is an advantage that the light emission can be sufficiently sustained by performing the role of increasing the light emission maintenance rate. In addition, when the second metal oxide having an average particle size of 30 to 500 nm is included in the self-luminous photosensitive resin composition, the light path can be increased by inducing sufficient light scattering. Accordingly, the light emission intensity can be made excellent, and a color filter having high luminance and light maintenance rate can be manufactured.

  When the average particle diameter of the scattering particles is less than the above range, for example, 10 nm, the scattering effect of incident light or light emitted from the quantum dots cannot be expected, and the scattering particles become too large beyond the above range. There is a problem that the surface of the self-luminous layer of uniform quality cannot be obtained because it sinks into the composition.

Therefore, in the present invention, both the first metal oxide having an average particle diameter of 100 to 500 nm and the second metal oxide having an average particle diameter of 30 to 500 nm are used as scattering particles, and the first metal oxide is By containing TiO ₂ and the second metal oxide containing ZnO, it is possible to effectively prevent oxidation of quantum dots generated during post-bake (PB) process as well as excellent light emission characteristics. Therefore, there is an advantage that a decrease in luminance occurring between processes can be reduced.

  In an embodiment of the present invention, a ratio of an average particle size 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 size of 100 to 500 nm, preferably 150 to 400 nm, as the scattering particles. In this case, the average particle size of the second metal oxide is It is preferable to use one having an average particle size of 0.1 to 0.5 times the average particle diameter of one metal oxide.

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

  In still 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 , Sn, Zr, Nb, Ce, Ta, and In may further include one or more metal oxides selected from In.

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

  In still another embodiment of the present invention, the first metal oxide is included in an amount of 50 to 90 parts by weight and the second metal oxide is less than 10 to 50 parts by weight with respect to 100 parts by weight of the solid content of the scattering particles. Can be. When the first metal oxide and the second metal oxide satisfy the above range, it is preferable because the effect of improving the light maintenance rate is excellent and a decrease in luminance can be suppressed. If the first metal oxide is less than the range, the light retention rate improvement effect may be insufficient, and if it exceeds the range, the brightness may decrease as the scattering effect decreases. It is preferable to use appropriately within the range. If the content of the second metal oxide is less than the above range, light scattering is difficult and the brightness improvement effect may be insufficient. If the content exceeds the above range, the improvement of the light maintenance rate may be hindered. It is preferable to use appropriately within the said range.

  The content of the scattering particles can be limited in the entire composition so that the emission intensity of the color filter can be sufficiently improved. Specifically, in still another embodiment of the present invention, the scattering particles are 0.1 to 50 parts by weight, preferably 0.3 to 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. May be included at ˜30 parts by weight. When the scattering particles are included in the above range, there is an advantage that a color filter having excellent emission intensity and stable performance can be produced. When the scattering particles are included below the range, it may be difficult to ensure the intended emission intensity, and when the range is exceeded, the effect of increasing the emission intensity is insufficient and the scattering particles are included. Since the stability of the self-luminous photosensitive resin composition can be lowered, it is preferably used within the above range.

  In still 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 contain a photopolymerizable compound. The photopolymerizable compound is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator, which will be described later, and is a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher polyfunctional monomer Examples include the body.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone. Examples of commercially available products include Aronix M-101 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S (manufactured by Nippon Kayaku Co., Ltd.), and Biscoat 158 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). It is not something.

  Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like are commercially available products such as Aronix M-210, M-1100, 1200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AH-600, AT-600 or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.) However, it is not limited to these.

  Specific examples of the trifunctional or higher polyfunctional monomer include 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 triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxyl Dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and commercially available products include ARONIX M-3 9, TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H but (manufactured by Nippon Kayaku Co., Ltd.) and the like, but it is not limited thereto.

  Examples of the photopolymerizable compound include dipentaerythritol (poly) acrylate having a hydroxyl group or a carboxylic acid group as shown in the following chemical formulas 1-2.

[Chemical Formula 1]

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

[Chemical formula 2]

In Formula 2, R _{3 to} R ₅ may be the same as or different from each other, and are OH, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group, or —OR ₇ , respectively.
R ₆ is —C (═O) CH ₂ CH ₂ C (═O) OH, R ₈ and R ₉ are acrylate groups or methacrylate groups, and R ₁₀ is hydrogen, acryloyl group, methacryloyl group or _{-C (= O) CH 2 CH} 2 C is (= O) OH.

  Of these, a polyfunctional monomer having two or more functional groups can be preferably used for the photopolymerizable compound of the present invention, and a carboxylic acid group-containing pentafunctional photopolymerizable compound can be more preferably used. The use of a polyfunctional monomer having five or more functional groups is preferable because the formation of a pixel pattern is further excellent. In particular, polyfunctional monomers containing five or more functional groups containing carboxylic acid groups have no photodegradation due to the aggregation of quantum dot particles and are excellent in photoreactivity. Can be formed.

  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 solid content of the self-luminous photosensitive resin composition. When the photopolymerizable compound is contained in less than the above range, it is preferable because the strength and smoothness of the pixel portion are improved. If the photopolymerizable compound is included in less than the range, the degree of photocuring by light may be reduced, and pixel pattern formation may be somewhat difficult, and if the range is exceeded, pattern peeling problems may occur. .

Alkali-soluble resin The self-luminous photosensitive resin composition of the present invention can contain an alkali-soluble resin. The alkali-soluble resin is a component that imparts solubility to an alkali developer used in the development process. In short, the alkali-soluble resin can perform the role of making the non-exposed part of the photosensitive resin layer formed using the self-luminous photosensitive resin composition alkali-soluble. In the present invention, the alkaline developer Any resin can be used without particular limitation as long as it is a resin that can be dissolved in water.

  Specifically, the alkali-soluble resin can be produced by copolymerizing one or more selected from an unsaturated monomer having a carboxyl group and a monomer having an unsaturated bond copolymerizable therewith. However, the present invention is not limited to this.

  As the unsaturated monomer having a carboxyl group, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated polyvalent carboxylic acid, or the like can be used.

  Specifically, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), Examples thereof include mono (2-acryloyloxyethyl) phthalate and mono (2-methacryloyloxyethyl) phthalate. The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These unsaturated monomers having a carboxyl group can be used alone or in admixture of two or more.

  Monomers having an unsaturated bond that can be copolymerized with the unsaturated monomer having a carboxyl group include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated monomers. Saturated carboxylic acid glycidyl ester compound, carboxylic acid vinyl ester compound, unsaturated ether compound, vinyl cyanide compound, unsaturated imide compound, aliphatic conjugated diene compound, giant unit having a monoacryloyl group or a monomethacryloyl group at the end of the molecular chain One or more selected from a monomer, a bulky monomer compound, and the like can be used.

More specifically, the monomer having an unsaturated bond capable of copolymerization includes styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, 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 vinylbenzyl 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-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl 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-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate Unsaturated carboxylic acid ester compounds such as norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl ester compounds such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
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, 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, vinylidene cyanide;
Unsaturated imide compounds such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; and polymer molecular chains of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane Macromonomers having a monoacryloyl group or a monomethacryloyl group at the end;
Bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton that can reduce the non-dielectric constant value can be used.

The alkali-soluble resin preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 200,000 in order to improve the surface hardness for use in a color filter, and is 5,000 to 100,000. It is more preferable that it is in the range. Moreover, it is preferable that it is 1.5-6.0, and, as for molecular weight distribution degree ( _Mw / _Mn ), it is more preferable that it is the range of 1.8-4.0. When the weight average molecular weight and molecular weight distribution of the alkali-soluble resin are within the above ranges, the hardness is improved, the remaining film ratio is high, the solubility of the unexposed part in the developer is excellent, and the resolution is improved. Can be made.

  The acid value of the alkali-soluble resin is preferably 20 to 200 mgKOH / g based on the solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary 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, the non-exposed part is easily dissolved, the sensitivity is increased, and as a result, the pattern of the exposed part remains during development. Thus, there is an advantage that the film remaining ratio is improved.

  The alkali-soluble resin may be contained in an amount 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 solid content in the self-light-emitting photosensitive resin composition. . When the content of the alkali-soluble resin is within the above-described range, the solubility in the developer is sufficient, and the non-pixel portion lackability is improved, so that a residue is hardly generated on the substrate, and the exposed portion is developed during development. This is preferable because film reduction of the pixel portion is prevented and pattern formation is facilitated. When the alkali-soluble resin is included in less than the range, some non-pixel portions may be missing, and when the alkali-soluble resin is included in excess of the range, the solubility in the developer is slightly decreased, Formation can be somewhat difficult.

Photopolymerization initiator The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention comprises the photopolymerizable compound described above by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates radicals that can initiate polymerization.

  As the photopolymerization initiator, those usually used in the art can be applied as long as the object of the present invention is not damaged, and the binder resin and the photopolymerizable compound can be polymerized. If possible, the type is not particularly limited. Representative examples include triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds. However, the present invention is not limited to these, and one or more types may be selected and used. it can.

  The light-emitting photosensitive resin composition containing the photopolymerization initiator is highly sensitive, and the pixel portion of the pixel pixel of the color filter formed with the light-emitting photosensitive resin composition has good strength and patternability. Therefore, the photopolymerization initiator is preferably included.

  Specifically, examples of the triazine compound include 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-triazine, 2,4-bis (trichloromethyl) -6- [2- (4 -Diethylamino-2-methyl Enyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. However, it is not limited to these.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl. ] -2-Methylpropan-1-one, 1-hydroxycyclohexyl phenyl 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] propan-1-one, 2- (4-methylbenzyl) -2 -(Dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. Moreover, the compound represented by following Chemical formula 3 is mentioned.

[Chemical formula 3]

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

  Examples of the compound represented by Chemical Formula 3 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) ) Propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2 -Amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2 Dimethylamino (4-morpholinophenyl) propane-1-one, such as 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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) -4,4′5,5′-tetraphenyl Examples thereof include -1,2′-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4 are more preferable. ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole may be used. it can.

  Examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-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-carbazol-3-yl) ethylidin) amino) oxy) eta Emissions, and the like, as commercially available products, but BASF Corp. OXE-01, OXE-02 and the like, but is not limited thereto. Moreover, following Chemical formula 4-6 etc. are mentioned.

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

  In addition, other photopolymerization initiators that are usually used can be further used within a range not damaging the effects of the present invention. Specific examples of the other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and other photopolymerization initiators. These can be used alone or in admixture of two or more.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone, 4′-di (N, N′-dimethylamino) -benzophenone and the like.

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

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

  Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenatrenequinone, camphorquinone, phenyl Examples include methyl glyoxylate and titanocene compounds.

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

  On the other hand, the photopolymerization initiator can be used in combination with a photopolymerization initiation auxiliary agent in order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention. Since the self-luminous photosensitive resin composition of the present invention contains a photopolymerization initiation auxiliary agent, the sensitivity is further increased, and productivity when forming a color filter using this composition can be improved. preferable.

  As the photopolymerization initiation auxiliary agent, for example, one or more compounds selected from amine compounds and carboxylic acid compounds can be preferably used.

  Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) Examples include benzophenone. As the amine compound, an aromatic amine compound is preferably used.

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

  The photopolymerization initiation auxiliary agent is preferably contained in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight based on the solid content in the self-luminous photosensitive resin composition. good. If the content of the photopolymerization initiation auxiliary 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 this composition tends to be improved. This is preferable.

Solvent The solvent contained in the self-luminous photosensitive resin composition according to the present invention is usually used in the art as long as it is effective to dissolve other components contained in the self-luminous photosensitive resin composition. The organic solvent to be used can be used without particular limitation. Examples of the solvent include ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters, and one or more types can be selected and used from these. Is not to be done.

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

  Specific examples of the acetate solvents include ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyls such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Ether acetates; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate;

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

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

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

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

  The said solvent can be used individually or in mixture of 2 or more types.

  Among the solvents, organic solvents having a boiling point of 100 to 200 ° C. are preferable from the viewpoint of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates; ketones; ethyl 3-ethoxypropionate, 3-methoxy And esters such as methyl propionate. These solvents can be used alone or in admixture of two or more.

  In the present invention, the content of the solvent is not particularly limited, and may include 60 to 90 parts by weight, more preferably 60 to 85 parts by weight, based on 100 parts by weight of the self-luminous photosensitive resin composition. Can be included. When the content of the solvent is within the above-mentioned range, the coating property is good when coated with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), or an ink jet. Can provide the effect. If the content of the solvent is less than the above range, the process may be somewhat difficult as the coating property is slightly reduced, and if the content exceeds the above range, the solvent is formed with the self-luminous photosensitive resin composition. In addition, there may be a problem that the performance of the color filter may be somewhat degraded.

Additives The self-luminous photosensitive resin composition according to the present invention includes additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers and anti-aggregation agents as necessary. Can further be included.

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

  Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based and positive surfactants. These can be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other than the above, as trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (MEGAFAC) (Dainippon Ink) Manufactured by Chemical Industry Co., Ltd.), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (SOLPERSE) ( Neka Co. production), EFKA (EFKA Chemicals Co. production), PB 821 (Ajinomoto production), and the like.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

  The additive can be appropriately added and used by those skilled in the art as long as the effects of the present invention are not impaired. For example, the additive is 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 self-luminous photosensitive resin composition. However, it is not limited to these.

<Color filter>
Still another embodiment of the present invention relates to a color filter manufactured with the above-described self-light-emitting photosensitive resin composition.

  When the color filter according to the present invention is applied to an image display device, it emits light by the light of the light source of the display device, so that it is possible to realize better light efficiency. In addition, since light having a hue is emitted, the color reproducibility is further improved, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

Specifically, the color filter according to the present invention includes a first metal oxide having an average particle size of 100 nm to 500 nm and a second metal oxide having an average particle size of 30 nm to 500 nm. a TiO _2, the second metal oxide, because it contains a cured product of the self-luminous light-sensitive resin composition is ZnO, excellent light maintenance factor, there is the advantage that is excellent in reflection brightness.

  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 the color filter itself, or may be a part where the color filter is located 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 is made of polyethersulfone (PES) or polycarbonate (PC). There may be.

  A pattern layer is a layer containing the photosensitive resin composition of this invention, Comprising: The layer formed by apply | coating the said photosensitive resin composition, exposure, image development, and thermosetting with a predetermined pattern may be sufficient. .

  The pattern layer formed of the self-luminous photosensitive resin composition comprises 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. can do. 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 irradiated with light. In this case, when applied to an image display device described later, the light emitted from the light source is not particularly limited, but it is preferable to use a light source that emits blue light from the viewpoint of better color reproducibility.

  In still 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 two kinds of hue pattern layers of a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the pattern layer is a transparent pattern layer that does not contain quantum dot particles. Can further be provided.

  When only the pattern layers of the two kinds of hues are provided, a light source that emits light having a wavelength indicating the remaining hue not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is to show blue.

  The color filter including the substrate and the pattern layer as described above may further include a barrier rib formed between the patterns 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>
Still another embodiment of the present invention relates to an image display device including the color filter described above. The color filter of the present invention can be applied not only to a normal liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

  The image display device according to the present invention is advantageous in that it has excellent light efficiency, high luminance, excellent color reproducibility, excellent reflection luminance, and a wide viewing angle.

  Hereinafter, the present specification will be described in detail with reference to examples. However, the examples according to the present specification may be modified in various other forms, and the scope of the present specification is not construed to be limited to the examples described in detail below. The examples herein are provided to more fully explain the present specification to those skilled in the art. In addition, “%” and “parts” indicating the content are based on weight unless otherwise specified.

Production Example 1 Synthesis of CdSe (core) / ZnS (shell) structure photoluminescent green quantum dot particles A CdO (0.4 mmol), zinc acetate (4 mmol), oleic acid (5.5 mL) Was placed in a reactor with 1-octadecene (20 mL) and heated to 150 ° C. for reaction. Thereafter, in order to remove acetic acid generated by replacing oleic acid with zinc, the reaction was left under a vacuum of 100 mTorr for 20 minutes. Thereafter, a heat of 310 ° C. was applied to obtain a transparent mixture, which was maintained at 310 ° C. for 20 minutes, and then 0.4 mmol of Se powder and 2.3 mmol of S powder were added to 3 mL of trioctylphosphine. The Se and S solution dissolved in was rapidly injected into the reactor containing the Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C. for 5 minutes, and then the growth was interrupted using an ice bath. Thereafter, the quantum dots are separated by precipitation with ethanol and the centrifuge is used to separate the quantum dots. The excess impurities are washed with chloroform and ethanol to stabilize the core particles stabilized with oleic acid. Quantum dot particles A having a CdSe (core) / ZnS (shell) structure in which particles having a total diameter and shell thickness of 3 to 5 nm were distributed were obtained.

Production Example 2 A flask equipped with an alkali-soluble resin synthesis stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was prepared, while N-benzylmaleimide 45 parts by weight, methacrylic acid 45 parts by weight, tricyclodecyl methacrylate 10 1 part by weight, 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 to the mixture and stirred to prepare a monomer dropping funnel. 6 parts by weight of dodecanediol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, dropping of the monomer and chain transfer agent from the dropping funnel was started. The dropwise addition was carried out for 2 hours each while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours, and then a gas introduction pipe was introduced to introduce oxygen / nitrogen = 5/95 (v Bubbling of the gas mixture was started. Next, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were charged into the flask and the temperature was 110 ° C. for 8 hours. The reaction was continued and then cooled to room temperature to obtain an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g.

Examples and Comparative Examples: Manufacture of Self-Luminous Photosensitive Resin Compositions Self-luminous photosensitive resin compositions according to Examples and Comparative Examples were manufactured with configurations and contents according to Tables 1 to 3 below. However, at this time, the first metal oxide and the second metal oxide were selected so that the scattering particles according to Table 1 below did not satisfy the scattering particles according to the present invention.

Production of Color Filter A color filter was produced using the self-luminous photosensitive resin composition produced according to the above-mentioned examples and comparative examples. Each of the self-luminous photosensitive resin compositions was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

  Next, a test photomask having a regular square transmission pattern of 20 mm × 20 mm in width and length and a line / space pattern of 1 to 100 μm is placed on the thin film, and the distance from the test photomask is set to 100 μm. Was irradiated.

At this time, the ultraviolet light source is irradiated with light at an exposure amount (365 nm) of 200 mJ / cm ² in an air atmosphere using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by USHIO ELECTRIC CO., LTD. Was not used.

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

Experimental Example 1: Measurement of a fine pattern Obtained through a line / space pattern mask designed to 100 μm among color filters manufactured using the self-luminous photosensitive resin compositions manufactured according to Examples and Comparative Examples. The pattern size was measured using an OM equipment (ECLIPSE LV100POL, manufactured by Nikon Corporation), and the difference from the design value of the line / space pattern mask is shown in Table 4 below.

  If 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 becomes difficult to implement fine pixels, and if it has a negative value, it means a critical value that causes a process failure. .

Experimental Example 2: Measurement of light emission intensity Of a color filter produced using the self-luminous photosensitive resin composition produced according to Examples and Comparative Examples, 365 nm was formed on a part formed with a regular square pattern of 20 × 20 mm. The light-converted area was measured using a Tube type 4W UV irradiator (VL-4LC, Vilber LOURMAT), and the emission intensity in the 450 nm area was measured using a spectrum meter (manufactured by Ocean Optics).

Higher measured emission intensity means higher light efficiency. Thus, referring to Table 5, Example 1 containing TiO ₂ having an average particle diameter of 100 nm to less than 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. It can be seen that ˜6 is superior in light emission luminance as compared with Comparative Examples 1 to 10 which do not satisfy this.

Experimental Example 3: Measurement of reflection luminance The color filter manufactured using the self-luminous photosensitive resin composition manufactured according to the example and the comparative example was externally formed on a portion formed with a regular square pattern of 20 × 20 mm. The reflection brightness by light was measured using an integrating sphere reflectometer (CM-3700D, Konika Minolta).

It means that the lower the measured reflection luminance, the better the visibility due to external light reflection. Accordingly, referring to Tables 4 and 6, the first metal oxide includes TiO ₂ having an average particle diameter of 100 nm to less than 500 nm and the second metal oxide includes ZnO having an average particle diameter of 30 nm to 500 nm or less. When Example 1-6 is not satisfy | filled, it turns out that it is difficult to satisfy | fill the light emission luminance, the fine pattern characteristic, and the visibility by external light reflection.

That is, Examples 1 to 6 containing TiO ₂ having an average particle diameter of 100 nm to less than 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 are fine patterns. It can be seen that measurement, emission intensity measurement and reflection luminance are all excellent.

In one embodiment of the present invention, the ratio of the average particle diameter of the first metal oxide and the second metal oxide is 0.1 to 0. 5 may be sufficient. Specifically, it is preferable to use a first metal oxide having an average particle size of 100 to 500 nm, preferably 150 to 400 nm, as the scattering particles. In this case, the average particle size of the second metal oxide is It is preferable to use one having an average particle size of 0.1 to 0.5 times the average particle diameter of one metal oxide.

In still 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 , Sn, Zr, Nb, Ta , and In may further include an oxide of one or more metals selected from In and In.

In still another embodiment of the present invention, 50 to 90 parts by weight of the first metal oxide and 10 parts by weight or more and less than 50 parts by weight of the second metal oxide with respect to 100 parts by weight of the total solid content of the scattering particles. Can be included. When the first metal oxide and the second metal oxide satisfy the above range, it is preferable because the effect of improving the light maintenance rate is excellent and a decrease in luminance can be suppressed. If the first metal oxide is less than the range, the light retention rate improvement effect may be insufficient, and if it exceeds the range, the brightness may decrease as the scattering effect decreases. It is preferable to use appropriately within the range. If the content of the second metal oxide is less than the above range, light scattering is difficult and the brightness improvement effect may be insufficient. If the content exceeds the above range, the improvement of the light maintenance rate may be hindered. It is preferable to use appropriately within the said range.

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 solid content of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included within the above range , it is preferable because the strength and smoothness of the pixel portion are improved. If the photopolymerizable compound is included in less than the range, the degree of photocuring by light may be reduced, and pixel pattern formation may be somewhat difficult, and if the range is exceeded, pattern peeling problems may occur. .

Claims (11)

Quantum dots; and scattering particles;
The scattering particles include: a first metal oxide having an average particle size of 100 nm to 500 nm; and a second metal oxide having an average particle size of 30 nm to 500 nm;
The first metal oxide is TiO ₂ ;
The self-luminous photosensitive resin composition, wherein the second metal oxide is ZnO.   2. The self-luminous photosensitive resin composition according to claim 1, wherein a ratio of an 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 according to claim 2, wherein a difference in average particle diameter between the first metal oxide and the second metal oxide is 60 nm or more.   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 The self-luminous photosensitive resin composition according to claim 1, further comprising one or more metal oxides selected from In and In. The further metal oxides include 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 The self-luminous photosensitive resin composition according to claim 4, which is at least one selected from MgO.   2. The self-luminous emission according to claim 1, which is contained in an amount of 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 solid content of the scattering particles. Photosensitive resin composition.   The self-luminous photosensitive resin composition according to claim 1, wherein the scattering particles are contained in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition.   The self-luminous photosensitive resin composition according to claim 1, further comprising one or more selected from the group consisting of a photopolymerizable compound, an alkali-soluble resin, a photopolymerization initiator, and a solvent.   The color filter containing the hardened | cured material of the self-light-emitting photosensitive resin composition in any one of Claims 1-8.   The color filter according to claim 9, wherein the color filter includes one or more selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. An image display device comprising the color filter according to claim 9.