TW201830141A - Photosensitive Resin Composition, Color Filter and Image Display Device - Google Patents

Abstract

The present invention provides a photosensitive resin composition comprising a photoluminescence quantum dot particle, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a photostabilizer and a solvent, wherein the photostabilizer includes a hindered amine compound, a color filter and an image display device prepared by using the same. The photosensitive resin composition according to the present invention maintains a high quantum efficiency without deteriorating luminescent property during a hard-bake process and exhibits excellent luminescent property.

Description

Photosensitive resin composition, color filter and image display device

The present invention relates to a photosensitive resin composition, a color filter, and an image display device. In particular, the present invention relates to a photosensitive resin composition which can maintain a high quantum efficiency during a hard baking process without deteriorating photoluminescence characteristics, and can exhibit excellent luminescent properties, and use of this A color filter of a photosensitive resin composition and an image display device.

The color filter is a thin film type optical element which can extract red, green and blue colors from white light, and can be used as a fine unit pixel, and the size of one pixel is several tens to several hundreds of micrometers. The color filter has a structure in which a black matrix layer having a predetermined pattern is formed on a transparent substrate to shield a boundary region between the respective pixels, and the pixel portions are sequentially stacked, wherein the plurality of colors are The three main colors (typically red (R), green (G), and blue (B)) are arranged in a predetermined pattern to form each pixel. In general, the color filter can be produced by coating three or more colors on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, or the like. In recent years, a pigment dispersion method using one of photosensitive resin-dispersed photosensitive resins has become mainstream.

A pigment dispersion method, which is one of methods for forming a color filter, is a method of forming a colored film by coating a photosensitive resin composition by repeating the following series of steps, the photosensitive resin composition including a An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and an additive, and a colorant are coated on a transparent substrate provided with a black matrix, and the pattern to be formed is exposed, and then a solvent is used. Unless it is exposed and thermally cured, it is very active in the manufacture of liquid crystal display (LCDs) for mobile phones, notebook computers, monitors, televisions, and the like. In recent years, the photosensitive resin composition used for the color filter produced by the pigment dispersion method having various advantages requires not only excellent pattern characteristics but also high color reproducibility and improved performance such as high luminance and high performance. Contrast and other performance.

However, the color reproducibility is achieved by the light irradiated by the light source penetrating through a color filter, in which a part of the light is absorbed by the color filter, thereby causing a decrease in luminous efficiency. Furthermore, due to the pigment characteristics of the color filter, there is a fundamental limitation that a perfect color reproducibility cannot be achieved.

As a solution to such a problem, there has been proposed a method of manufacturing a color filter in which a color filter is produced using a photosensitive resin composition including quantum dots (Korean Patent Publication No. 10-2016- Rev. 0086739). In this example, the illuminating waveform is narrowed by using quantum dots, exhibiting a high ability to achieve light color without being able to pass through the pigment, and excellent luminescent properties. However, there is a problem in this manner that quantum dots are oxidized during a hard baking process under high temperature operation in the manufacture of a color filter, thereby causing a decline in luminous efficiency. Therefore, the need to develop a method that can suppress the above problems arises.

Technical problem to be solved

An object of the present invention is to provide a photosensitive resin composition which can maintain a high quantum efficiency during a hard baking process without deteriorating luminescent properties and exhibits excellent luminescent properties. .

Another object of the present invention is to provide a color filter using a photosensitive resin composition.

Still another object of the present invention is to provide an image display device having a color filter.

Solution

In another aspect, the present invention provides a photosensitive resin composition comprising a photoluminescence quantum dot particle, a photopolymerizable compound, a photopolymerization initiator, and a photopolymerization initiator. An alkali-soluble resin, a photostabilizer, and a solvent, wherein the light stabilizer comprises a hindered amine compound.

In one embodiment of the present invention, the hindered amine compound is represented by the following Chemical Formula 1.

[Chemical Formula 1]

among them,

R _a and R _b are each independently hydrogen or methyl;

R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl;

R _e is hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkene Alkenyl, C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3- C12 cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 Cycloalkenyloxy, C6-C20 aryl substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, C1-C4 alkyl or C1-C4 alkoxy or halogen a substituted or unsubstituted C6-C20 aryloxy group; an alkylcarbonyl group selected from the group consisting of -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2 -C19 alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _{6- 10} aryl), C6-C10 arylcarbonyl (-C(=O)-C _6-10 aryl), C1-C6 alkyl ester group (-C(=O)-OC _1-6 alkyl), C6 -C10 aryl ester group (-C(=O)-OC _6-10 aryl), C1-C6 alkylaminocarbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl guanamine (-C(=O)-N(C _1-6 alkyl) ) _2), acyl (acyl); or the alkyl is selected from C1-C19 acyl group _{(-OC (= O) -C 1-19} alkyl), C2-C19 alkenyl group of the acyl group (-OC (=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _6-10 aryl) acyloxy;

Y is -O-C(=O)-R'-C(=O)-O-;

R' is a C1-C10 alkyl group, a C3-C12 cycloalkyl group, a C6-C15 aryl group or ;as well as

R" is a C1-C10 alkyl group, a C3-C12 cycloalkyl group or a C6-C15 aryl group.

In one embodiment of the present invention, the hindered amine compound is represented by the following Chemical Formula 2.

[Chemical Formula 2]

among them,

R is ;

R _a and R _b are each independently hydrogen or methyl;

R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl;

R _e is hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkene Alkenyl, C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3- C12 cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 Cycloalkenyloxy, C6-C20 aryl substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, C1-C4 alkyl or C1-C4 alkoxy or halogen a substituted or unsubstituted C6-C20 aryloxy group; an alkylcarbonyl group selected from the group consisting of -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2 -C19 alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _{6- 10} aryl), C6-C10 arylcarbonyl (-C(=O)-C _6-10 aryl), C1-C6 alkyl ester group (-C(=O)-OC _1-6 alkyl), C6 -C10 aryl ester group (-C(=O)-OC _6-10 aryl), C1-C6 alkylaminocarbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl guanamine (-C(=O)-N(C _1-6 alkyl) ) _2), acyl (acyl); or the alkyl is selected from C1-C19 acyl group _{(-OC (= O) -C 1-19} alkyl), C2-C19 alkenyl group of the acyl group (-OC (=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _6-10 aryl) acyloxy.

In one embodiment of the present invention, the light stabilizer may further comprise at least one light stabilizer selected from the group consisting of a benzotriazole-based photostabilizer, a triazine-based photostabilizer. And a group consisting of benzophenone-based photostabilizers.

On the other hand, the present invention provides a color filter formed using the above-described photosensitive resin composition.

In another aspect, the present invention provides an image display device comprising the above-described color filter.

Excellent effect

The photosensitive resin composition according to the present invention comprises a hindered amine compound as a light stabilizer, which can suppress oxidation of photoluminescent quantum dot particles during a hard baking process, and thus does not deteriorate photoluminescence characteristics. A high quantum efficiency can be maintained and excellent luminescent properties can be exhibited.

The invention will be described in more detail below.

One embodiment of the present invention relates to a photosensitive resin composition comprising a photoluminescence quantum dot particle (A), a photopolymerizable compound (B), and a photopolymerization initiation. Photopolymerization initiator (C), an alkali-soluble resin (D), a photostabilizer (E) and a solvent (F), wherein the aforementioned light stabilizer comprises a hindered amine compound (hindered amine compound).

Photoluminescence quantum dot particles (A)

The photosensitive resin composition of the present invention includes photoluminescent quantum dot particles.

Quantum dots are semiconductor materials of nanometer size. Atoms form molecules, and a plurality of molecules form aggregates composed of a plurality of small molecules, which are called clusters to form nanoparticles. When such nanoparticles have semiconductor properties, they are referred to as quantum dots.

When a quantum dot absorbs energy from the outside and causes the quantum dot to enter an excited state, the quantum dot releases its own energy corresponding to the energy band gap.

The photosensitive resin composition of the present invention includes, for example, photoluminescent quantum dot particles, and therefore a color filter prepared by using the photosensitive resin composition can emit light by photoilishing (photoluminescence).

In a conventional image display device including a color filter, white light passes through the color filter to present color. In this process, since a part of the light is absorbed by the color filter, the light efficiency is lowered. However, when a color filter is prepared using the photosensitive resin composition according to the present invention, when the color filter is irradiated with light of a light source, the color filter spontaneously emits light, thereby achieving superior illumination. effectiveness.

Furthermore, since color light is emitted, color reproducibility is excellent, and light rays are emitted in all directions due to photoluminescence, the viewing angle can also be improved.

The quantum dot particles according to the present invention are not particularly limited as long as the equivalent sub-point particles are excited by light to emit light. For example, the quantum dot may be selected from the group consisting of a II-VI semiconductor compound, a III-V semiconductor compound, an IV-VI semiconductor compound, a group IV element or a compound containing a group IV element, and any combination thereof. The group, and these compounds may be used singly or in combination of two or more.

The above II-VI semiconductor compound may be a binary compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; selected from CdSeS, CdSeTe, a ternary compound of a group consisting of CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and selected from CdZnSeS, CdZnSeTe a quaternary compound of the group consisting of CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. The above III-V semiconductor compound may be a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; a ternary compound of a group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof; and selected from GaAlNP, GaAlNAs, A quaternary compound of a group consisting of GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The above IV-VI semiconductor compound may be a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS a ternary compound of a group consisting of SnPbSe, SnPbTe, and a mixture thereof; and a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof. The above Group IV element or compound containing a Group IV element may be a compound selected from the group consisting of Si, Ge, and mixtures thereof; and a binary compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The quantum dots may have a homogeneous single structure; a double structure such as a core-shell structure, a gradient structure, and the like; or a mixture of the foregoing structure.

In the double structure of a core-shell structure, the respective materials constituting the core and the shell may be composed of the above different types of semiconductor compounds, respectively. For example, the core may include at least one material selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but the invention is not limited thereto. The shell may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but the invention is not limited thereto.

A color photosensitive resin composition for preparing a typical color filter includes red, green, and blue coloring agents to exhibit color. Further, the photoluminescence quantum dot particles can be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. The quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.

The quantum dot particles can be synthesized using a wet chemical process, a metal organic chemical vapor deposition process, or a molecular beam epitaxy process.

A wet chemical process is a method of adding a precursor material to an organic solvent to grow particles. When the crystal grains grow, the organic solvent naturally coordinates to the surface of the quantum dot crystal grains to act as a dispersing agent, thereby controlling the growth of the crystal grains. Thus, the growth of nanoparticles can be controlled by an easier and less expensive process than vapor deposition, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE).

The content of the photoluminescence quantum dot particles is not particularly limited. For example, the content of the photoluminescence quantum dot particles may be, for example, 3% to 80% by weight based on 100% by weight of the total solid content of the photosensitive resin composition. Percentage, or for example 5% to 70% by weight. If the content of the photoluminescent quantum dot particles is less than 3% by weight, the luminous efficiency may be insufficient. If the content of the photoluminescent quantum dot particles exceeds 80% by weight, the content of other components may be relatively insufficient, and it is difficult to form a single pixel pattern.

Photopolymerizable compound (B)

The photopolymerizable compound contained in the photosensitive resin composition of the present invention is a compound which can be polymerized by the action of light and one of photopolymerization initiators described later, and includes a monofunctional monomer, a difunctional monomer, and the like. Functional monomers and analogs thereof.

Some specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-B. 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like.

Some specific examples of difunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate (ethyleneglycol di (meth)acrylate), neopentyllglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, bisphenol A Bis(acryloyloxyethyletherether bisphenol A), 3-methylpentandiol di(meth)acrylate, and the like.

Some specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol. Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Dipentaerythritol pentaacrylate succinic acid monoester and analogs thereof.

Among the above monomers, a difunctional monomer or a polyfunctional monomer is preferably used.

The content of the photopolymerizable compound may be in the range of 5% to 50% by weight, for example, 7% to 45% by weight, based on 100% by weight of the total solid content of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is preferable to favor the strength and smoothness of the pixel portion to be good.

Photopolymerization initiator (C)

The photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited and may be selected from the group consisting of a triazine-based compound and an acetophenone-(acetophenone- And a compound of at least one of the group consisting of a compound, a biimidazole-based compound, and an oxime compound. The photosensitive resin composition containing the above photopolymerization initiator (C) has high sensitivity, and the composition is used to form a single pixel whose pixel portion has relatively good intensity and smoothness.

Further, when the photopolymerization initiator (C) is used together with a photopolymerization initiation auxiliary agent (C-1), the photosensitive resin composition containing the two becomes more sensitive. The degree of productivity of the color filter formed using the composition is therefore improved.

For example, the triazine compound is, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine (2,4-bis (trichloromethyl) )-6-(4-methoxyphenyl)-1,3,5-triazine), 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl-1,3,5-triazine), 2,4-bis(trichloromethyl)-6-piperidin-1,3,5 - 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl) -1,3,5-triazine (2,4-bis(trimethoxymethyl)-6-(4-methoxystyryl)-1,3,5-triazine), 2,4-bis(trichloromethyl)-6- [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine (2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) Ethenyl]-1,3,5-triazine), 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine (2 , 4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine), 2,4-bis(trichloromethyl)-6-[2-( 4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine (2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) )ethenyl]-1,3,5-triazine), 2 , 4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine (2,4-bis(trichloromethyl)- 6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine) and its analogs.

For example, the acetophenone compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methyl-1) -phenylpropan-1-one), benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one (2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one), 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4) -Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl 2-[2-(1-methylvinyl)phenyl]propan-1-one (2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one) Oligomers of their analogs. Further, it is also possible to include a compound represented by Chemical Formula 3.

[Chemical Formula 3]

among them,

R ₁ to R ₄ are each independently hydrogen, halogen, monohydroxy, substituted or unsubstituted phenyl with C1 to C12 alkyl, substituted or unsubstituted benzyl with C1 to C12 alkyl, Or a naphthyl group substituted or unsubstituted with an alkyl group of C1 to C12.

Some specific examples of the compound represented by the above Chemical Formula 3 include 2-methyl-2-amino(4-morpholinophenyl). Ethan-1-one), 2-ethyl-2-amino(4-morpholinophenyl)ethan-1-one 2-propyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-butyl- 2-butyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-methyl-2-amino group (4 -Methyl-2-amino(4-morpholinophenyl)propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) 2-methyl-2-amino(4-morpholinophenyl)butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl)propan-1-one ( 2-ethyl-2-amino(4-morpholinophenyl)propan-1-one), 2-ethyl-2-amino (4-morpholinophenyl)butan-1-one (2-ethyl-2- Amino(4-morpholinophenyl)butan-1-one), 2-methyl-2-methylamino(4-morpholinophenyl)propan-1-one (2-methyl-2-methylamino(4-morpholinophenyl) Propan -1-one), 2-methyl-2-dimethylamino(4-morpholinophenyl)propan-1-one ), 2-methyl-2-diethylamino(4-morpholinophenyl)propan-1-one and the like Things.

For example, a biimidazole-based compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole), 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyl 2,2'-bis(2,3-dichlorophenyl-4,4',5,5'-tetraphenylbiimidazole), 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetra(4-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialoxyphenyl)biimidazole (2,2'-bis(2-chlorophenyl)-4,4',5, One of the 4'-tetra(trialkoxyphenyl)biimidazole), 4,4',5,5' positions, the phenyl group is substituted with an imidazole compound, and the like. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) can be preferably used. Phenyl)-4,4',5,5'-tetraphenylbiimidazole.

For example, the oxime compound is, for example, a compound represented by the following Chemical Formula 4, Chemical Formula 5 or Chemical Formula 6 or the like.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Further, other photopolymerization initiators and the like which are generally used in the art can be further used without impairing the effects of the present invention. Other photopolymerization initiators include, for example, a benzoin-based compound, a benzophenone-based compound, an anthracene-based compound, and a thioxanthone. A thioxanthone-based compound, and an analog thereof; and these compounds may be used alone or in combination of two or more.

The above benzoin compounds are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzene. Benzoin isobutyl ether, and its analogs.

The above benzophenone compounds are, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzene. 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone (3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone), 2,4,6-trimethylbenzophenone, 4,4'-di N,N'-Dimethylamino)-benzophenone (4,4'-di(N,N'-dimethylamino)-benzophenone), and analogs thereof.

The above thioxanthone-based compound, for example, 2-isopropylthioxantone, 2,4-diethylthioxantone, 2,4 - 2,4-dichlorothioxantone, 1-chloro-4-propoxythioxantone, and analogs thereof.

The above anthracene-based compound is, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene (2-ethyl-9) ,10-dimethoxyanthracene), 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and its analog.

Other photopolymerization initiators mentioned above are, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 10-butyl-2-chloroacridine Ketone (10-butyl-2-chloroacridone), 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate (methyl phenylglyoxylate), a titanocene compound, and the like.

Further, in the present invention, when a photopolymerization initiation auxiliary agent (C-1) is used together with the photopolymerization initiator (C), it is preferably used selected from an amine compound. And at least one compound of the group consisting of carboxylic acid compounds.

Specific examples of the amine compound in the above photopolymerization initiating auxiliary include, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, or triisopropanolamine. And analogs thereof; an aromatic amine compound such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (ethyl 4- Dimethylaminobenzoate), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-benzoic acid 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (4 4'-bis(dimethylamino)benzophenone, commonly known as: Michler's ketone, (4,4'-bis(diethylamino)benzophenone) and the like. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the above carboxylic acid compound include aromatic heteroacetic acids such as phenylthioacetic acid, methylphenylthioacetic acid, and ethylphenylthio Ethyl acetate (ethylphenylthioacetic acid), methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid (phenoxyacetic acid), naphthylthioacetic acid, N-naphthylglycine, naphthoxy acetic acid, and the like.

The content of the photopolymerization initiator (C) may be in the range of 0.1% to 20% by weight, for example, 1% to 10% by weight, based on 100% by weight of the total solid content of the photosensitive resin composition. between. The content of the photopolymerization initiating auxiliary (C-1) may be in the range of 0.1% to 20% by weight, for example, 1% to 10, based on 100% by weight of the total solid content of the photosensitive resin composition. Between % weight percentage.

When the content of the photopolymerization initiator (C) is within the above range, since the photosensitive resin composition is highly sensitive, it is advantageous in the intensity of the pixel portion or the smoothness of the surface of the pixel portion. In addition, when the content of the photopolymerization initiation auxiliary (C-1) is within the above range, the sensitivity efficiency of the photosensitive resin composition is further improved, and the productivity of the color filter formed using the composition is also More improved.

Alkali-soluble resin (D)

The alkali-soluble resin (D) can be polymerized by including a carboxyl group-containing ethylenically unsaturated monomer. When the pattern is formed, the alkali-soluble resin is a component having solubility for one of the alkaline developing solutions used in the developing process.

The above-mentioned ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and the like. Analogs thereof; dicarboxylic acids, such as fumaric acid, mesaconic acid, itaconic acid, and one of the foregoing anhydrides; A mono(meth)acrylate of a polymer of one hydroxyl group, such as ω-carboxy polycaprolactone mono(meth)acrylate and the like. Preferably, it may be acrylic acid and methacrylic acid. They may be used singly or in combination of two or more.

The alkali-soluble resin according to the present invention may further comprise at least one other monomer copolymerizable with the aforementioned monomer to carry out polymerization. Examples thereof may include an aromatic vinyl compound such as styrene, vinyl toluene, methyl styrene, p-chlorostyrene, ortho-methyl O-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether Ether), m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether , m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like; an N-substituted maleimide compound (N -substituted maleimide-based compound, such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide (N -phenylmaleimide), N-o-hydroxyphenyl maleimide (No-hydroxyphenylmaleimid) e), N-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenyl mala No-methylphenylmaleimide, N-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o- No-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide (Np-methoxyphenylmaleimide) and its analogues; alkyl (meth) acrylate, such as methyl (meth) acrylate, ethyl (meth) acrylate (ethyl(meth)acrylate), n-propyl(meth)acrylate,i-propyl(meth)acrylate,(meth)acrylic acid N-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl(meth)acrylate, (A) T-butyl (meth)acrylate and its Like; alicyclic (meth) acrylate, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) Acrylate), 2-methylcyclohexyl(meth)acrylate, tricyclo[5.1.01.0 ^2,6 ]non-8-yl ester (tricyclo[ 5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate), 2-dicyclopentanyloxyethyl(meth)acrylate, (meth)acrylate Isobornyl (meth)acrylate and its analogues; aryl (meth)acrylate, such as phenyl (meth)acrylate, (methyl) Benzyl methacrylate and its analogues; an unsaturated oxetane compound such as 3-(methacryloxymethyl)oxetane 3-(methacryloyloxymethyl)oxetane), 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane Methyl)-2-trifluoromethyl 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane (2-(methacryloyloxymethyl)-4-trifluoromethyloxetane) and its analogs. They may be used singly or in combination of two or more.

The (meth) acrylate used herein means an acrylate or a monomethacrylate.

The content of the alkali-soluble resin is not particularly limited, and for example, 100% by weight based on the total solid content of the photosensitive resin composition, and the content of the alkali-soluble resin may be in the range of 5% to 80% by weight, for example, Between 10% and 70% by weight of the range. If the content of the alkali-soluble resin is within the above range, the solubility in an alkaline developing solution is sufficient, so that a pattern is easily formed, and the film of the exposed pixel portion in development can be prevented from being reduced, so that the non-pixel portion can be improved. Solubility.

Light stabilizer (photostabilizer) (E)

The light stabilizer includes a hindered amine compound. The photosensitive resin composition of the present invention comprises a hindered amine compound which inhibits photoluminescence of quantum dot particles from being oxidized during a hard baking process, thereby maintaining a high quantum efficiency without degrading photoluminescence characteristics. (luminescent property) and can exhibit excellent photoluminescence properties.

In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following Chemical Formula 1.

[Chemical Formula 1]

Wherein R _a and R _b are each independently hydrogen or methyl;

R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl;

R _e is hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkene Alkenyl, C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3- C12 cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 Cycloalkenyloxy, C6-C20 aryl substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, C1-C4 alkyl or C1-C4 alkoxy or halogen a substituted or unsubstituted C6-C20 aryloxy group; an alkylcarbonyl group selected from the group consisting of -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2 -C19 alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _{6- 10} aryl), C6-C10 arylcarbonyl (-C(=O)-C _6-10 aryl), C1-C6 alkyl ester group (-C(=O)-OC _1-6 alkyl), C6 -C10 aryl ester group (-C(=O)-OC _6-10 aryl), C1-C6 alkylaminocarbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl guanamine (-C(=O)-N(C _1-6 alkyl) ) _2), acyl (acyl); or the alkyl is selected from C1-C19 acyl group _{(-OC (= O) -C 1-19} alkyl), C2-C19 alkenyl group of the acyl group (-OC (=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _6-10 aryl) acyloxy;

Y is -O-C(=O)-R'-C(=O)-O-;

R' is a C1-C10 alkyl group, a C3-C12 cycloalkyl group, a C6-C15 aryl group or ;as well as

R" is a C1-C10 alkyl group, a C3-C12 cycloalkyl group or a C6-C15 aryl group.

In one embodiment of the present invention, the hindered amine compound may be a compound represented by the following Chemical Formula 2.

[Chemical Formula 2]

among them,

R is ;

R _a and R _b are each independently hydrogen or methyl;

R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl;

R _e is hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkene Alkenyl, C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3- C12 cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 Cycloalkenyloxy, C6-C20 aryl substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, C1-C4 alkyl or C1-C4 alkoxy or halogen a substituted or unsubstituted C6-C20 aryloxy group; an alkylcarbonyl group selected from the group consisting of -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2 -C19 alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _{6- 10} aryl), C6-C10 arylcarbonyl (-C(=O)-C _6-10 aryl), C1-C6 alkyl ester group (-C(=O)-OC _1-6 alkyl), C6 -C10 aryl ester group (-C(=O)-OC _6-10 aryl), C1-C6 alkylaminocarbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl guanamine (-C(=O)-N(C _1-6 alkyl) ) _2), acyl (acyl); or the alkyl is selected from C1-C19 acyl group _{(-OC (= O) -C 1-19} alkyl), C2-C19 alkenyl group of the acyl group (-OC (=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _6-10 aryl) acyloxy.

The alkyl group referred to in the present invention includes a straight chain or a chain, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, N-octyl, n-decyl and the like.

Further, the alkenyl group is an alkyl group having at least one carbon-carbon double bond, and the alkynyl group is an alkyl group having at least one carbon-carbon triple bond.

The aryl group referred to in the present invention includes phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthrene. Phhenthroyl, pyrenyl and analogs thereof.

The cycloalkyl group referred to in the present invention includes cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, damantyl, and substituted. And substituted and unsubstituted boronyl, norbornyl and norbornenyl.

The alkoxy group referred to in the present invention includes methoxy, ethoxy, n-propoxy, i-propoxy, tert-butoxy. (t-butoxy), n-butoxy, pentoxy and the like.

The acyl referred to in the present invention may be, for example, a formyl, an acetyl group, a trifluoroacetyl group, a pivaloyl group, or an acryloyl group. , methacryloyl, oleoyl, cinamoyl, benzoyl, 2,6-xyloyl, tert-butyl Tert-butoxycarbonyl, ethylcarbamoyl, phenylcarbamoyl and the like.

The acyloxy group may be acetoxy, trifluoroacetoxy, pivaloyloxy, acryloyloxy, methacryloxyl ( Methacryloyloxy), benzoyloxy and its analogs.

In Chemical Formula 1, R _a , R _b , R _c and R _d may be hydrogen, R _e may be hydrogen or a C1-C18 alkoxy group, and Y may be -OC(=O)-R'-C(=O ) -O-, and R' may be a C1-C10 alkyl group.

In Chemical Formula 2, R _a , R _b , R _c and R _d may be hydrogen, and R _e may be hydrogen or a C1-C18 alkyl group.

Commercially available products of the compound represented by Chemical Formula 1 include, for example, TINUVIN 123, TINUVIN 770DF, TINUVIN 292 (BASF, trade name), and the like.

Commercially available products of the compound represented by Chemical Formula 2 include, for example, LA-52, LA-57 (trade name, manufactured by Adeka Co., Ltd.), and the like.

Further, in addition to the hindered amine compound, the light stabilizer further comprises at least one known light stabilizer. For example, the light stabilizer may further comprise a benzotriazole-based photostabilizer, a triazine-based photostabilizer, and a benzophenone light stabilizer (benzophenone). -based photostabilizer) at least one light stabilizer of the group consisting of.

As the benzotriazole-based light stabilizer, a known benzotriazole derivative can be used, and it can be taken from a commercially available product. Specific examples include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5' -(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5-di-tert-butylphenyl) 2-(2'-hydroxy-3',5-di-tert-butylphenylbenzotriazole), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (2 -(2'-hydroxy-5'-tert-octylphenyl)benzotriazole) or 2-(2'-hydroxy-3',5'-di-tert-octylphenyl)benzotriazole (2-(2'-hydroxy) -3',5'-di-tert-octylphenyl)benzotriazole); commercially available products include, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUBIN 571, TINUVIN 900, TINUVIN 928 or TINUVIN 1130 (BASF Manufacturing company, the name of the product).

As the triazine-based light stabilizer, a hydroxyphenyl triazine-based ultraviolet absorber can be preferably used. And it can be obtained from a commercially available product. Examples include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 or TINUVIN 1577 (manufactured by BASF Corporation, trade name) and the like.

As the benzophenone-based light stabilizer, a known benzophenone derivative can be used, and it can be taken from a commercially available product. Specific examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone (2-hydroxy-4-n-) Octyloxybenzophenone), 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone (2-hydroxy-4) -benzyloxybenzophenone), 5,5'-bis(2-hydroxyyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'- 2,2'-dihydroxy-4-methoxybenzophenone or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2 '-dihydroxy-4,4'-dimethoxybenzophenone), and commercially available products include, for example, CHIMASSORB 81 (manufactured by BASF Corporation, trade name) and the like.

The additional light stabilizer may be added in an amount of from 0.2 part by weight to 2 parts by weight of the additional light stabilizer per 1 part by weight of the hindered amine compound.

The content of the light stabilizer may be, for example, in the range of 0.025% to 10% by weight, for example, in the range of 0.01% to 7% by weight, based on 100% by weight of the total solid content of the photosensitive resin composition. between. When the content of the light stabilizer is within the above range, deterioration of the light-emitting efficiency of the photosensitive resin composition can be avoided, and a pattern can be appropriately formed without interfering with the action of the photopolymerization initiator.

Solvent (F)

The solvent of the present invention is not particularly limited and may be an organic solvent conventionally used.

Specific examples of the solvent may include ethyleneglycol monoalkylether such as ethyleneglycolmonomethylether, ethyleneglycolmonoethylether, ethyleneglycol monopropylether (ethyleneglycolmonopropylether) ), ethyleneglycol monobutylether and its analogues; diethyleneglycoldialkylether, such as diethyleneglycoldimethylether, diethylene glycol diethyl Diethyleneglycoldiethylether, diethyleneglycoldipropylether, diethyleneglycoldibutylether and the like; ethyleneglycolalkyletheracetate, such as ethylene glycol Methyl etherosolveacetate, ethylcellosolveacetate and the like; propylene glycol monoalkyl ether (propyleneglycol monoalkylether), such as propylene glycol monomethyl ether (propyleneglycolmonomethylether) and its analogues; alkylene Alcohol alkyl ether acetate Eneglycolalkyletheracetate), for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate (propyleneglycol monoethyl ether acetate), propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxybutyl acetate Methoxypentylacetate and its analogues; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like; ketones such as methylethylketone, acetone , methylamylketone, methylisobutylketone, cyclohexanone and the like; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol , ethyleneglycol and glycerin and the like; esters such as 3-ethoxypropionic acid ethyl, methyl 3-methoxypropionate (3-methoxypropionic acid methyl) and analogs thereof; cyclic esters such as γ-butyrolactone and the like. These solvents may be used singly or in combination of two or more.

The content of the solvent is not particularly limited and may be, for example, the weight of the total solid content relative to the photosensitive resin composition, and the solvent content may be in the range of 60% to 90% by weight, for example, 70% to 85% by weight. Between the ranges. If the content of the solvent is within the above range, preferred coating properties are obtained.

The photosensitive resin composition of the present invention may further include the additive (G) as needed. For example, fillers, other polymer compounds, adhesion promoters, anti-agglomeration agents, and the like can be used as the additive.

Fillers include, for example, glass, cerium oxide, aluminum oxide, and the like.

Other polymer compounds, specifically, may include a thermosetting resin such as an epoxy resin, a maleimide resin, and the like; a thermoplastic resin such as polyvinyl alcohol or polyacrylic acid. Acid), polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) decane (vinyltris (2-methoxyethoxy)) may be mentioned. Silane), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl 3-methacryloxypropyltrimethoxysilane, 3-巯Trimethoxy Silane (3-mercaptopropyltrimethoxysilane) and the like.

As the anti-coagulant, specific examples are, for example, sodium polyacrylate and the like.

One embodiment of the present invention relates to a color filter manufactured using the photosensitive resin composition of the present invention.

When the color filter of the present invention is applied to an image display device, it emits light by being excited by light emitted from a light source of the display device, thereby achieving more excellent luminous efficiency. Furthermore, since the color light is emitted, the color reproducibility is very good, and since the light is emitted in all directions due to photoluminescence, the viewing angle can also be improved.

The color filter may include a substrate and a patterned layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion for providing the color filter on the display device, or the like; and thus is not particularly limited. For example, the substrate may include glass, silicon (Si), silicon oxide (SiO _x) or a polymer substrate. The polymer substrate may, for example, comprise polyether oxime (PES) or polycarbonate (PC).

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

In an embodiment of the invention, the pattern layer formed of the photosensitive resin composition can provide a red pattern layer containing red quantum dot particles, including green quantum dot particles. A green pattern layer or a blue pattern layer comprising blue quantum dot particles. When illuminated with light, 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. In this example, when the pattern layer is applied to an image display device, the light emitted from the light source is not particularly limited, but a more excellent color reproducibility can be achieved by using a light source that emits blue light.

In an embodiment of the invention, the pattern layer may be a pattern layer including only two of the red pattern layer, the green pattern layer, and the blue pattern layer. In this example, the pattern layer may further comprise a transparent pattern layer that does not contain quantum dot particles. In the case where only two color pattern layers are provided, the wavelength at which a light source emits light can be used to represent the remaining color not included. 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 blue light passes through the transparent The pattern layer is blue.

As described above, the color filter may include, in addition to the substrate and the pattern layer, a barrier layer formed between the associated patterns, and may further include a black matrix. Moreover, the color filter may further include a protective film formed on the pattern layers.

An embodiment of the invention relates to an image display device including the aforementioned color filter.

The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices, such as an electroluminescence display device, a plasma display device, and a field. A field emission display device and the like.

Hereinafter, more details of the present invention will be described by way of the following examples, comparative examples and experimental examples. However, the examples, comparative examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Preparation Example 1: Synthesis of photoluminescent green quantum dot particles having a CdSe (nuclear)/ZnS (shell) structure

0.4 mmol of CdO, 4 mmol of zinc acetate and 5.5 mL of oleic acid were placed in a reactor together with 20 mL of 1-octadecene, and then heated to 150 ° C and allowed to react. Then, the above reaction mixture was allowed to stand in a vacuum of 100 mTorr for 20 minutes to remove acetic acid formed by substituting zinc with oleic acid. Thereafter, the reaction mixture was heated to 310 ° C to obtain a clear mixture, and then the transparent mixture was kept at 310 ° C for 20 minutes. Then, a solution of Se and S, including 0.4 mmol of Se powder and 2.3 mmol of S powder, was dissolved in 3 mL of trioctylphosphine, and rapidly injected with Cd(OA) ₂ and Zn (OA). ) ₂ of the solution in a reactor. The resulting mixture was grown at 310 ° C for 5 minutes and then allowed to grow to stop using an ice bath. Next, precipitation was carried out in ethanol, and then a quantum dot was separated using a centrifuge, and additional impurities were washed away with chloroform and ethanol, thereby obtaining a quantum dot having a CdSe (nuclear)/ZnS (shell) structure and stabilized with oleic acid. Wherein the quantum dot particles have a total of a core particle diameter and a shell thickness of 3 to 5 nm.

Preparation Example 2: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. Separately, 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, and 4 parts by weight of t-butyl-2-ethyl peroxide T-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) were stirred and mixed in a flask to prepare a monomer drop. Further, 6 parts by weight of n-dodecyl mercaptan and 24 parts by weight of PGMEA were added and stirred and mixed to prepare a chain transfer agent drip. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and after the air in the flask was replaced with nitrogen, the temperature of the flask was raised to 90 ° C while stirring. Next, the monomer drip and the chain transfer agent drip were added dropwise by means of a dropping funnel. The step of dropping dropwise for 2 hours was carried out under the conditions of maintaining 90 ° C, respectively. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then introduced into a gas introduction tube to start bubble blowing of an oxygen/nitrogen=5/95 (v/v) mixed gas. Next, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (2,2'- Methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask, and the reaction was continued at 110 ° C for 8 hours. Thereafter, the reaction was 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 1-7 and Comparative Examples 1-2: Preparation of Photosensitive Resin Compositions

The components (units) to be mixed are shown in Table 1, and then diluted with propylene glycol monomethyl ether acetate to have a total solid content of 20% by weight, and sufficiently stirred to obtain a photosensitive resin composition. .

【Table 1】

A-1: Quantum dots of the CdSe (nuclear)/ZnS (shell) structure of Preparation Example 1

B-1: dipentaerythritol pentaacrylate succinic acid monoester (pentafunctional photopolymerizable compound containing a carboxylic acid) (trade name TO-1382, manufactured by Dong-A)

B-2: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by NIPPON KAYAKU Co., Ltd.)

C-1: Irgaqure-907 (manufactured by BASF)

D-1: alkali-soluble resin of Preparation Example 2

E-1: TINUVIN 123 (manufactured by BASF) - hindered amine compound (a compound of Chemical Formula 1, wherein R _a , R _b , R _c and R _d are hydrogen, R _e is octyloxy, and Y is -OC(=O) -R'-C(=O)-O-, and R' is octyl)

E-2: TINUVIN 770DF (manufactured by BASF) - hindered amine compound (a compound of Chemical Formula 1, wherein R _a , R _b , R _c and R _d are hydrogen, R _e is hydrogen, and Y is -OC(=O)-R '-C(=O)-O-, and R' is octyl)

E-3: LA-52 (manufactured by ADEKA) - hindered amine compound (a compound of formula 2, wherein R _a , R _b , R _c and R _d are hydrogen and R _e is a methyl group)

E-4: LA-57 (manufactured by ADEKA) - hindered amine compound (a compound of formula 2, wherein R _a , R _b , R _c and R _d are hydrogen and R _e is hydrogen)

E-5: TINUVIN 109 (manufactured by BASF) - benzotriazole compound

E-6: DABCO (1,4-diazabicyclo[2.2.2]octane) (1,4-diazabicyclo[2,2,2]octane)

Experimental example 1

A color filter was prepared as follows by using the photosensitive resin compositions prepared in the examples and the comparative examples. Here, the development speed, sensitivity, and adhesion were measured by the following methods, and the measurement results are summarized in Table 2 below.

<Preparation of color filter>

Each of the above photosensitive resin compositions was separately coated on a glass substrate by a spin coating method, then placed on a hot plate, and maintained at a temperature of 100 ° C for 3 minutes to form a film. Next, a square light transmission pattern having a length and a width of 20 mm x 20 mm and a test mask having a line/space pattern of 1 μm to 100 μm were placed on the film, and the film was placed 100 μm apart from the test mask. Distance and then ultraviolet light.

Among them, an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Denki was used as an ultraviolet light source, and light irradiation was performed at an exposure amount (365 nm) of 200 mJ/cm ² without using a special optical filter. The film irradiated with ultraviolet rays was immersed in an aqueous KOH solution having a pH of 10.5 for 80 seconds, and then developed. The glass plate coated with the film 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. The color filter manufactured above had a film thickness of 3.0 μm.

(1) Pattern accuracy

Regarding the color filter obtained by using the photosensitive resin composition, the pattern size obtained by passing through a reticle having a line/space pattern of 100 μm was measured by an OM instrument (model ECLIPSE LV100POL, Nikon). A pattern error can be calculated by comparing the width of the light-transmitting pattern with the measured width of the color filter (measured pattern width). That is, the pattern error can be obtained by the following Equation 1.

[Equation 1]

Pattern error (Δ) = (width of light transmission pattern) - (width of measurement pattern)

If the value of the pattern error is larger than 20 mm, it is difficult to form a fine pattern, which also makes it difficult to form a fine pixel. If the value of the pattern error is a negative value, a process defect may occur.

(2) Luminescence intensity and luminous intensity retention (heat resistance)

A pattern portion of a color filter having a square pattern of 20 mm x 20 mm was irradiated using a 365 nm tubular 4W UV lamp (Model: VL-4LC, manufactured by VILBER LOURMAT). The light intensity in the wavelength (550 nm) region emitted by photoluminescence was measured using a spectrometer (manufactured by OCEAN OPTICS Co.).

Further, a hard bake step of 60 minutes was carried out at 230 ° C, and the measurement of the luminescence intensity was performed before and after the hard baking, and the luminescence intensity retention ratio was compared with Comparative Example 1. The results are shown in Table 2 below.

【Table 2】

As shown in Table 2, the results confirmed that the photosensitive resin composition of Comparative Examples 1 and 2 did not include a light stabilizer, and the photosensitive resin composition including the hindered amine compound according to Examples 1 to 7 of the present invention, Among them, the hindered amine compound as a light stabilizer can indeed realize the production of a fine pattern; and the present invention can suppress the oxidation of the quantum dot particles, and the luminescent intensity can be maintained to a higher level even after the hard baking process.

While the invention has been described in detail hereinabove, it will be apparent to those skilled in the art that the specific embodiments of the present invention are only a preferred embodiment, and the scope of the present invention is not limited thereto. Furthermore, as the skilled artisan understands, various applications and retouchings are possible without departing from the spirit and scope of the invention as described above.

Therefore, the scope of the invention is defined by the scope of the appended claims and their equivalents.

no

no

Claims (9)

A photosensitive resin composition comprising a photoluminescence quantum dot particle, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin (alkali-soluble) And a solvent, wherein the light stabilizer comprises a hindered amine compound. The photosensitive resin composition according to claim 1, wherein the hindered amine compound is represented by the following Chemical Formula 1: [Chemical Formula 1] Wherein R _a and R _b are each independently hydrogen or methyl; R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl; R _e is Hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkenyl (alkenyl) ), C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3-C12 ring Cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 cycloalkoxy Cycloalkenyloxy, C6-C20 aryl group substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, substituted by C1-C4 alkyl or C1-C4 alkoxy or halogen or not Substituted aryloxy of C6-C20; alkylcarbonyl selected from -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2-C19 Alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _6-10 aryl) , C6-C10 arylcarbonyl group of _{(-C (= O) -C 6-10} aryl), C1-C6 Alkyl ester group _{(-C (= O) -OC 1-6} alkyl), C6-C10 aryl group of the ester group _{(-C (= O) -OC 6-10} aryl), C1-C6 alkylamino of Carbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl An aryl group (-C(=O)-N(C _1-6 alkyl) ₂ ); or an alkyloxy group selected from C1-C19 (-OC(=O)-C _1-19 alkyl), C2-C19 alkenyloxy (-OC(=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _{6- 10} aryl) acyloxy; Y is -OC(=O)-R'-C(=O)-O-;R' is a C1-C10 alkyl group, a C3-C12 cycloalkyl group, C6-C15 aryl or And R" is a C1-C10 alkyl group, a C3-C12 cycloalkyl group or a C6-C15 aryl group. The photosensitive resin composition according to claim 1, wherein the hindered amine compound is represented by the following Chemical Formula 2: [Chemical Formula 2] Where R is And R _a and R _b are each independently hydrogen or methyl; R _c and R _d are each independently hydrogen, C1-C4 alkyl or C6-C10 aryl; and R _e is Hydrogen, C1-C18 alkyl, C1-C18 alkoxy, C2-C7 alkyl substituted by hydroxy or C2-C7 alkoxy, C2-C18 alkenyl (alkenyl) ), C2-C18 alkenyloxy, C3-C18 alkynyl, C3-C18 alkynyloxy, C3-C12 cycloalkyl, C3-C12 ring Cycloalkoxy, C6-C10 bicycloalkyl, C6-C10 bicycloalkoxy, C3-C8 cycloalkenyl, C3-C8 cycloalkoxy Cycloalkenyloxy, C6-C20 aryl group substituted or unsubstituted by C1-C4 alkyl or C1-C4 alkoxy or halogen, substituted by C1-C4 alkyl or C1-C4 alkoxy or halogen or not Substituted aryloxy of C6-C20; alkylcarbonyl selected from -C(=O)-H, C1-C19 (-C(=O)-C _1-19 alkyl), C2-C19 Alkenylcarbonyl (-C(=O)-C _2-19 alkenyl), C6-C10 aryl C2-C4 alkenylcarbonyl (-C(=O)-C _2-4 alkenyl-C _6-10 aryl) , C6-C10 arylcarbonyl group of _{(-C (= O) -C 6-10} aryl), C1-C6 Alkyl ester group _{(-C (= O) -OC 1-6} alkyl), C6-C10 aryl group of the ester group _{(-C (= O) -OC 6-10} aryl), C1-C6 alkylamino of Carbonyl (-C(=O)-NH-C _1-6 alkyl), C6-C10 arylaminocarbonyl (-C(=O)-NH-C _6-10 aryl) and C1-C6 alkyl An aryl group (-C(=O)-N(C _1-6 alkyl) ₂ ); or an alkyloxy group selected from C1-C19 (-OC(=O)-C _1-19 alkyl), C2-C19 alkenyloxy (-OC(=O)-C _2-19 alkenyl) and C6-C10 aryloxy (-OC(=O)-C _{6- 10} aryl) acyloxy. The photosensitive resin composition according to claim 2, wherein R _a , R _b , R _c and R _d are hydrogen, R _e is hydrogen or a C1-C18 alkoxy group, and Y is -OC (= O)-R'-C(=O)-O-, and R' is an alkyl group of C1-C10. The photosensitive resin composition according to claim 3, wherein R _a , R _b , R _c and R _d are hydrogen, and R _e is hydrogen or a C1-C18 alkyl group. The photosensitive resin composition according to claim 1, wherein the light stabilizer further comprises at least one light stabilizer selected from the group consisting of a benzotriazole-based photostabilizer and a triazine. A group consisting of a triazine-based photostabilizer and a benzophenone-based photostabilizer. The photosensitive resin composition according to claim 1, wherein the light stabilizer is contained in an amount of from 0.025% to 10% by weight based on 100% by weight based on the total solid content of the photosensitive resin composition. A color filter is formed using the photosensitive resin composition according to any one of claims 1 to 7. An image display device comprising the color filter as described in claim 8 of the patent application.