KR102748931B1 - Self emission type photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention relates to a self-luminous photosensitive resin composition for producing a color filter and an image display device which exhibit excellent fluorescence efficiency without a separate color conversion layer, by including a fluorescent dye having an emission wavelength range of 520 to 700 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm; and a color filter and an image display device produced using the same.

Description

SELF EMISSION TYPE PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND IMAGE DISPLAY DEVICE USING THE SAME

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

Recently, the display industry has rapidly changed from CRT (Cathode-Ray Tube) to flat panel displays represented by PDP (Plasma Display Panel), OLED (Organic Light-Emitting Diode), and LCD (Liquid-Crystal Display). Among them, LCD is widely used as a visual display device in almost all industries, and its application range is continuously expanding.

In LCD, white light generated from a backlight unit passes through liquid crystal cells, adjusts its transmittance, and mixes the three primary colors that pass through red, green, and blue color filters to implement full color.

The backlight unit uses a CCFL (Cold Cathode Fluorescent Lamp) as a light source, but in this case, the backlight unit must always supply power to the CCFL, which causes problems with power consumption. In addition, the color reproducibility is about 70% of that of existing CRTs, and environmental pollution problems due to the addition of mercury are pointed out as disadvantages.

To solve the above problems, research is currently being actively conducted on backlight units using LEDs (Light Emitting Diodes) as an alternative.

When LEDs are used as backlight units, they can provide consumers with more vivid picture quality by exceeding 100% of the NTSC (National Television System Committee) color reproduction range specifications.

Accordingly, in the same industry, methods are being proposed to improve the efficiency of backlight sources by changing the materials and structures of color filters and LCD panels.

Color filters form pixels of each color by applying a dispersion composition containing pigments or dyes and then through a patterning process. However, these pigments and dyes cause the problem of reducing the transmission efficiency of a backlight light source. This reduction in transmission efficiency ultimately lowers the color reproducibility of the display device, making it difficult to implement a high-quality screen.

The problem of low color reproducibility can be solved by increasing the light efficiency of the color filter, and thus, a method of increasing the thickness of the color filter or introducing a color conversion layer (or light conversion layer) by laminating it or in proximity to it has been proposed.

In this regard, Korean Patent Publication No. 2010-0056437 discloses a method of forming a color conversion layer on a color filter layer using an inkjet method to absorb light of a specific wavelength and output light having a wavelength different from the absorbed wavelength, and Korean Patent Publication No. 2012-0048218 discloses a color filter including a light-changing portion containing a fluorescent material.

However, methods such as the above have the problem that the process becomes complicated and the process time becomes long because the compositions for forming the color filter layer and the color conversion layer must be created separately.

Republic of Korea Publication Patent No. 2010-0056437 (May 27, 2010) Republic of Korea Publication Patent No. 2012-0048218 (May 15, 2012)

The present invention is intended to solve the above problems, and the purpose of the present invention is to provide a self-luminous photosensitive resin composition for manufacturing a color filter and an image display device, which comprises only a color conversion layer without including a color filter layer, thereby simplifying the process of manufacturing a color filter and an image display device, and thereby shortening the process time, and also having excellent fluorescence efficiency, and an image display device including the same.

In addition, the present invention aims to provide a color filter and an image display device including a cured product of the aforementioned self-luminous photosensitive resin composition.

To achieve the above object, the self-luminous photosensitive resin composition of the present invention is characterized by including a fluorescent dye having an emission wavelength range of 520 to 750 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm.

In addition, the color filter according to the present invention is characterized by including a cured product of the aforementioned self-luminous photosensitive resin composition.

In addition, the image display device according to the present invention is characterized by including the color filter described above.

The self-luminous photosensitive resin composition according to the present invention comprises a fluorescent dye having an emission wavelength range of 520 to 750 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm; thereby having an advantage in that a color filter and an image display device can be manufactured by replacing the role of a color filter layer with only a color conversion layer without including a separate color filter layer and also having excellent fluorescence efficiency.

In addition, when manufacturing a color filter and an image display device using the self-luminous photosensitive resin composition according to the present invention, the process can be simplified and the process time can be shortened by forming a single-layer color conversion layer that does not include a separate color filter layer, and the color conversion layer alone can replace the role of the color filter layer, and there is also the advantage of excellent fluorescence efficiency.

Figure 1 is a schematic diagram of a color filter including a conventional color filter layer and a color conversion layer.
Figure 2 is a schematic diagram of a color filter including only a color conversion layer of the present invention.

In the present invention, when it is said that a certain member is located "on" another member, this includes not only a case where a certain member is in contact with another member, but also a case where another member exists between the two members.

When it is said that a part of the present invention "includes" a certain component, this does not exclude other components, unless otherwise specifically stated, but rather means that other components may be included.

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

< Self-luminous Photosensitive resin composition>

According to one embodiment of the present invention, a self-luminous photosensitive resin composition comprises a fluorescent dye having an emission wavelength range of 520 to 750 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm; thereby replacing the role of a color filter layer without a separate color filter layer, and has an advantage in that a color filter and an image display device exhibiting excellent fluorescence efficiency can be manufactured. In addition, since a process step for forming a separate color filter layer is unnecessary when manufacturing a color filter and an image display device using the composition, there is an advantage in that the overall process step can be simplified, thereby shortening the process time.

Fluorescent dye

A self-luminous photosensitive resin composition according to one embodiment of the present invention comprises a fluorescent dye having an emission wavelength range of 520 to 750 nm.

According to one embodiment of the present invention, the fluorescent dye may be at least one selected from the group consisting of cyanine-based, xanthine-based, pyridine-based, low-molecular-weight luminescent materials, and high-molecular-weight luminescent materials.

The fluorescent dye may be, more specifically, at least one selected from the group consisting of cyanine fluorescent dyes including 4-dicyano-methylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM-1(I)), DCM-2(II), DCJTB(III), etc.; xanthine fluorescent dyes including rhodamine B and rhodamine 6G, etc.; pyridine fluorescent dyes including pyridine 1; low-molecular-weight luminescent materials such as 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene(Ⅳ), Lumogen F Red, Nile Red(V), etc.; and high-molecular-weight luminescent materials including polyphenylene, polyarylene, polyfluorene, etc., but is not limited thereto.

According to one embodiment of the present invention, the fluorescent dye may be included in an amount of 0.1 to 70 wt%, preferably 1 to 40 wt%, based on 100 wt% of the total self-luminous photosensitive resin composition. If the content of the fluorescent dye is less than the above range, luminous efficiency cannot be secured, and thus the color conversion characteristics desired in the present invention cannot be sufficiently secured. If the content exceeds the above range, the luminous efficiency improvement effect relative to the content of the fluorescent dye is insignificant, and thus the manufacturing cost of the color conversion filter may increase.

Pigment

A self-luminous photosensitive resin composition according to one embodiment of the present invention comprises a pigment having a maximum absorption wavelength range of 380 to 500 nm.

The above pigments can be used without limitation as long as they satisfy the above-mentioned maximum absorption wavelength range, and specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 63, 83, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc. can be mentioned, but are not limited thereto.

According to one embodiment of the present invention, the pigment may be included in an amount of 0.1 to 70 wt%, preferably 1 to 40 wt%, based on 100 wt% of the total fluorescent dye included.

When the pigment is included within the above range, there is an advantage of excellent fluorescence efficiency. In addition, when the pigment exceeds the content range, the fluorescence efficiency may be reduced.

The above pigment can be used in the form of a pigment dispersion in which the particle size is uniformly dispersed. An example of a method for uniformly dispersing the particle size of the pigment is a method of dispersing by containing a dispersant and a solvent, and according to this method, a pigment dispersion composition in which the pigment is uniformly dispersed in the solution can be obtained. At this time, the solvent may be a solvent described below.

The above dispersant is added to de-agglomerate and maintain stability of the insoluble colorant, and any of those commonly used in the field can be used without limitation. Specifically, cationic, anionic, nonionic, amphoteric, polyester, polyamine, and other surfactants can be mentioned, and each of these can be used alone or in combination of two or more.

Commercially available products of the dispersant include, for example, BYK's DISPER BYK-101, DISPER BYK-103, DISPER BYK-107, DISPER BYK-108, DISPER BYK-110, DISPER BYK-111, DISPER BYK-112, DISPER BYK- 116, DISPER BYK-130, DISPER BYK-140, DISPER BYK-142, DISPER BYK-154, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-165, DISPER BYK-166, DISPER BYK-167, DISPER BYK-168, DISPER BYK-170, DISPER BYK-171, DISPER BYK-174, DISPER BYK-180, DISPER BYK-181, DISPER BYK-182, DISPER BYK-183, DISPER BYK-184, DISPER BYK-185, DISPER BYK-190, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2009, DISPER BYK-2010, DISPER BYK-2020, DISPER BYK-2025, DISPER BYK-2050, DISPER BYK-2070, DISPER BYK-2095, DISPER BYK-2150, DISPER BYK-2155, DISPER BYK-2163, DISPER BYK-2164, etc., Lubrizol SOLSPERSE-3000 from the company, SOLSPERSE-9000, SOLSPERSE-13000, SOLSPERSE-13240, SOLSPERSE-13650, SOLSPERSE-13940, SOLSPERSE-16000, SOLSPERSE-17000, SOLSPERSE-18000, SOLSPERSE-20000, SOLSPERSE-21000, SOLSPERSE-24000, SOLSPERSE-26000, SOLSPERSE-27000, SOLSPERSE-28000, SOLSPERSE-31845, SOLSPERSE-32000, SOLSPERSE-32500, SOLSPERSE-32550, SOLSPERSE-33500, SOLSPERSE-32600, SOLSPERSE-34750, SOLSPERSE-35100, Examples include SOLSPERSE-36600, SOLSPERSE-38500, SOLSPERSE-41000, SOLSPERSE-41090, SOLSPERSE-53095, SOLSPERSE-55000, SOLSPERSE-56000, and SOLSPERSE-76500.

These may be used alone or in combination of two or more, and specifically, at least one selected from the group consisting of DISPERSE BYK-2000, DISPERSE BYK-2001, SOLSPERSE-3000, SOLSPERSE-21000, SOLSPERSE-26000, SOLSPERSE-36600, and SOLSPERSE-4000, which are dispersants having an acidic functional group, may be used.

The above dispersant may be included in an amount of 5 to 60 parts by weight, specifically 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the insoluble colorant included together in the self-luminous photosensitive resin composition. If the content of the dispersant exceeds the above range, the viscosity of the colored photosensitive resin composition including it may increase, and if it is included in an amount less than the above range, it may be difficult to atomize the insoluble colorant included together or problems such as gelation after dispersion may occur.

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further include at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.

Alkali soluble resin

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further include an alkali-soluble resin.

The above alkali-soluble resin typically has reactivity under the action of light or heat and alkali solubility, and acts as a dispersion medium for coloring materials (fluorescent dyes, pigments, etc.). The above alkali-soluble resin acts as a binding resin for coloring materials (fluorescent dyes, pigments, etc.) included in the self-luminous photosensitive resin composition of the present invention, and can be used without limitation as long as it is soluble in an alkaline developer used in the developing step for producing a color filter.

Specifically, the alkali-soluble resin may include at least one selected from the group consisting of a polymer of an unsaturated monomer containing a carboxyl group, a copolymer with a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof.

At this time, the unsaturated monomer containing a carboxyl group may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, etc. Specifically, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. Unsaturated dicarboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. The unsaturated polycarboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid include maleic anhydride, itaconic anhydride, citraconic anhydride, etc. In addition, the unsaturated polycarboxylic acid may be its mono(2-methacryloyloxyalkyl)ester, and examples thereof include mono(2-acryloyloxyethyl) succinic acid, mono(2-methacryloyloxyethyl) succinic acid, mono(2-acryloyloxyethyl) phthalic acid, and mono(2-methacryloyloxyethyl) phthalic acid. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, and examples thereof include monoacrylate, monomethacrylate, and omega-carboxypolycaprolactone. These carboxyl group-containing monomers may be used alone or in mixtures of two or more.

In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer may be at least one selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, carboxylic acid vinyl ester compounds, unsaturated ether compounds, cyanide vinyl compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, macromonomers having a monoacryloyl group or monomethacryloyl group at the terminal of the molecular chain, bulky monomers, and combinations thereof.

More specifically, the copolymerizable monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene, etc.; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butylacrylate, n-butyl methacrylate, i-butylacrylate, i-butyl methacrylate, sec-butylacrylate, sec-butyl methacrylate, t-butylacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutylacrylate, 2-Hydroxybutyl methacrylate, 3-Hydroxybutyl methacrylate, 3-Hydroxybutyl methacrylate, 4-Hydroxybutyl acrylate, 4-Hydroxybutyl methacrylate, Allyl acrylate, Allyl methacrylate, Benzyl acrylate, Benzyl methacrylate, Cyclohexylacrylate, 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, Methoxypropylene glycol acrylate, Unsaturated carboxylic acid esters such as methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 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, and vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and polysiloxane; Bulky monomers such as a monomer having a norbornyl skeleton capable of lowering the dielectric constant, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton can be used.

The above alkali-soluble resin can be selected and used as having an acid value of 20 to 200 (KOHmg/g). The above "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, is related to solubility, and can be typically obtained by titration using a potassium hydroxide aqueous solution. When the acid value of the above alkali-soluble resin satisfies the above range, the solubility in a developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity increases, and as a result, the pattern of the exposed portion remains during development, so that there is an advantage that the film remaining ratio can be improved.

It is preferable that the polystyrene-converted weight average molecular weight (hereinafter referred to as “weight average molecular weight”) of the alkali-soluble resin as measured by gel permeation chromatography (GPC; using tetrahydrofuran as a dissolution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. When the weight average molecular weight of the alkali-soluble resin satisfies the above range, there are advantages of improving the film retention rate, excellent solubility of non-exposed portions in a developer, and improved resolution.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the above alkali-soluble resin may be 1.5 to 6.0, preferably 1.8 to 4.0. When the molecular weight distribution satisfies the above range, there is an advantage of improved developability.

The alkali-soluble resin may be included in an amount of 5 to 85 wt%, preferably 10 to 70 wt%, based on 100 wt% of the total solid content of the self-luminous photosensitive resin composition containing it. When the content of the alkali-soluble resin satisfies the above range, the solubility in a developer is sufficient, so that the occurrence of development residue on the substrate in the non-pixel portion can be suppressed, and the film reduction in the pixel portion of the exposed portion is prevented during development, so that there is an advantage of good omission properties in the non-pixel portion.

Photopolymerization Compound

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further include a photopolymerizable compound.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and may include a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers.

The type of the above monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.

The type of the above bifunctional monomer is not particularly limited, and examples thereof include 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, and 3-methylpentanediol di(meth)acrylate.

The type of the above polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. Among these, polyfunctional monomers having two or more functions are preferably used.

The photopolymerizable compound may be included in an amount of 5 to 50 wt%, specifically 7 to 45 wt%, based on 100 wt% of the total solid content of the self-luminous photosensitive resin composition containing the same. When the photopolymerizable compound is included within the above range, there is an advantage in that the intensity or smoothness of the pixel portion is improved. That is, when the photopolymerizable compound is included in an amount less than the above range, the intensity of the pixel portion may be somewhat reduced, and when the photopolymerizable compound is included in an amount exceeding the above range, the smoothness may be somewhat reduced, and therefore it is preferable that the photopolymerizable compound is included within the above range.

Photopolymerization Initiator

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further contain a photopolymerization initiator.

From the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., it is preferable to use as the photopolymerization initiator at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds.

Specific examples of the above acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

Examples of the above benzophenone compounds include benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of the above triazine compounds 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, Examples thereof include 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

Specific examples of the above biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 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-1,2'-biimidazole, or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

Specific examples of the above oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and representative commercial products include BASF's Irgacure OXE 01 and OXE 02.

Examples of the above thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

The above photopolymerization initiator may be included in an amount of 0.1 to 40 wt%, preferably 1 to 30 wt%, based on the total 100 wt% of the alkali-soluble resin and the photopolymerizable compound based on the solid content.

The photopolymerization initiator may be included in an amount of 0.1 to 20 wt%, preferably 0.5 to 15 wt%, and more preferably 1 to 10 wt%, based on 100 wt% of the total solid content of the self-luminous photosensitive resin composition. When the photopolymerization initiator is included within the above range, the self-luminous photosensitive resin composition becomes highly sensitive, thus shortening the exposure time, thereby improving productivity and maintaining high resolution, which is preferable. In addition, there is an advantage in that the strength of a pixel portion formed using the self-luminous photosensitive resin composition according to the present invention and the smoothness on the surface of the pixel portion become good.

The above photopolymerization initiator may further include a photopolymerization initiation assistant in order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention. When the above photopolymerization initiation assistant is included, the sensitivity is further increased, thereby providing the advantage of improved productivity.

The photopolymerization initiation assistant may preferably be one or more compounds selected from the group consisting of, for example, amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group, but is not limited thereto.

As the above amine compound, it is preferable to use an aromatic amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like can be used.

The above carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compounds having the above thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), etc.

Examples of commercially available products of the above photopolymerization initiation aid include EAB-F (Hodogaya Chemical Industry Co., Ltd.), and the above photopolymerization initiation aid may be appropriately added and used within a range that does not impair the scope of the present invention.

The content of the photopolymerization initiation assistant may be 10 moles or less, preferably 0.01 to 5 moles, per 1 mole of the photopolymerization initiator included together. When the photopolymerization initiation assistant is included within the content range, the sensitivity of the self-luminous photosensitive resin composition including it is improved, and the productivity of the color filter manufactured using the self-luminous photosensitive resin composition is improved, which is advantageous.

solvent

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further contain a solvent.

The above solvent is not particularly limited, and an organic solvent commonly used in the field can be used.

The solvents above specifically include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Examples thereof include ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

The above solvent is preferably an organic solvent having a boiling point of 100°C to 200°C among the above solvents in terms of applicability and drying property, more preferably an alkylene glycol alkyl ether acetate, a ketone, an ester such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate, and even more preferably a propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. These solvents can be used alone or in mixtures of two or more.

The solvent may be included in an amount of 60 to 90 wt%, preferably 70 to 85 wt%, based on 100 wt% of the total weight of the self-luminous photosensitive resin composition. When the content of the solvent is included within the above range, the coating property may be improved when applied by a coating device such as a roll coater, a spin coater, a slit-and-spin coater, a slit coater (sometimes called a die coater), or an inkjet, which is preferable. That is, when the content of the solvent is included below the above range, the coating property may be somewhat reduced, making the process somewhat difficult, and when it exceeds the above range, the performance of the color filter formed with the self-luminous photosensitive resin composition may be somewhat reduced, which may cause a problem.

Additives

A self-luminous photosensitive resin composition according to one embodiment of the present invention may further contain an additive.

The above additives may be added according to the needs of those skilled in the art within a range that does not harm the purpose of the present invention, and specifically, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulants, etc. may be mentioned.

Specific examples of the above fillers include, but are not limited to, glass, silica, alumina, etc.

Specific examples of the other polymer compounds include, but are not limited to, curable resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

Specific examples of the above adhesion accelerators include, but are not limited to, vinyltrimethoxysilane, miniltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. no.

The antioxidant may be included in an amount of 1 to 100 parts by weight, specifically 2 to 50 parts by weight, based on the solid content, per 100 parts by weight of the photopolymerization initiator included together. When the content of the antioxidant satisfies the above range, an effect of improving the transmittance can be expected without a decrease in the sensitivity of the colored photosensitive resin composition. When the content of the antioxidant is less than the above range, it is difficult to expect an effect of improving the transmittance, and when it exceeds the above range, the sensitivity may be lowered, which may cause a short circuit of the pattern during the developing process.

Specific examples of the above ultraviolet absorbent include, but are not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone, etc.

Specific examples of the above anti-coagulant include, but are not limited to, sodium polyacrylate.

The above additives can be used alone or in combination of two or more.

<Color Filter>

Another aspect of the present invention relates to a color filter including a color conversion layer manufactured using the aforementioned self-luminous photosensitive resin composition.

The color filter according to the present invention includes a color conversion layer made of a self-luminous photosensitive resin composition including a fluorescent dye having an emission wavelength range of 520 to 700 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm; thereby exhibiting excellent fluorescence efficiency without including a separate color filter layer, and having an advantage of replacing the roles of existing color filter layers and color conversion layers with only a single-layer configuration of the color change layer.

In addition, compared to the conventional manufacturing process of laminating a color conversion layer (20) and a color filter layer (30) on a substrate (10), the color filter of the present invention directly laminates the color conversion layer (20) on the substrate (10), so that a separate color filter layer (30) is not formed, and therefore the manufacturing process for forming the color filter layer (30) is excluded, so that the manufacturing process of the color filter can be simplified, and thus there is an advantage in that the process time is shortened (see FIGS. 1 and 2).

The above color filter includes a substrate and a pattern layer formed on top of the substrate.

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

The above pattern layer is a layer including the self-luminous photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminous photosensitive resin composition and exposing, developing, and thermally curing it in a predetermined pattern. The pattern layer can be formed by performing a method commonly known in the art.

A color filter including a substrate and a pattern layer as described above may further include partitions formed between each pattern, and may further include a black matrix, but is not limited thereto.

Additionally, it may further include a protective film formed on top of the pattern layer of the color filter.

The above color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. The red pattern layer, the green pattern layer, and the blue pattern layer may each emit red light, green light, and blue light when irradiated with light. At this time, the light emitted from the light source is not particularly limited, but a light source that emits blue light may be used in terms of better color reproducibility.

<Video display device>

Another aspect 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 to various image display devices such as conventional liquid crystal display devices, full luminescence display devices, plasma display devices, and field emission display devices.

The above image display device includes a color filter including a cured product of a self-luminous photosensitive resin composition including a fluorescent dye and pigment of the present invention, so that the color conversion layer alone can replace the roles of the color filter layer and the color conversion layer without a separate color filter layer, and has the advantage of exhibiting excellent fluorescence efficiency. In addition, since the process of forming a separate color filter layer is excluded in the manufacturing process of the image display device, the manufacturing process of the image display device can be simplified, and thus, there is an advantage of shortening the process time.

According to one embodiment of the present invention, the image display device may further include a light source, and specifically, the light source may be one that emits blue light. In the case of an image display device that does not require a light source (for example, an OLED), this does not matter, but in the case of including a light source as described above, the wavelength of light emitted from the light source (for example, 400 to 480 nm in the case of blue light) and the wavelength emitted from the fluorescent dye included in the color conversion layer may be mixed with each other, which may cause a problem in that the fluorescence efficiency of the fluorescent dye is reduced. However, the self-luminous photosensitive resin composition according to one aspect of the present invention has an advantage in that it absorbs the wavelength emitted from the light source and only the wavelength emitted by the fluorescent dye is displayed, that is, the fluorescence efficiency of the fluorescent dye is not reduced, by also including a pigment having a maximum absorption wavelength range of 380 to 550. Therefore, the self-luminous photosensitive resin composition according to one aspect of the present invention is most preferable when applied to an image display device including a light source.

Hereinafter, the present invention will be described in detail by way of examples in order to specifically explain the present invention. However, the examples according to the present invention can be modified in various different forms, and the scope of the present invention is not construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those with average knowledge in the art. In addition, "%" and "part" indicating the content below are based on weight unless specifically stated.

Manufacturing example 1: Preparation of alkali-soluble resin (C)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared, and meanwhile, as a monomer dropping funnel, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyltoluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were introduced and mixed to prepare, and as a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred to prepare a mixture. Thereafter, 385 g of PGMEA was introduced into the flask, and the atmosphere inside the flask was replaced from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Subsequently, dropwise addition of the monomer and the chain transfer agent was started from the dropping funnel. The addition was carried out for 2 h each while maintaining the temperature at 90°C, and after 1 h, the temperature was raised to 110°C and maintained for 3 h. Then, a gas introduction tube was introduced to initiate bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v). Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of the acrylic acid used in this reaction)], 0.4 g of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 g of triethylamine were charged into the flask, and the reaction was continued at 110°C for 8 hours, to obtain an alkali-soluble resin (C) having a solid acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene as measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the above binder resin were measured using the GPC method under the following conditions.

Device: HLC-8129GPC (manufactured by Dosoh Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 ㎕

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

Example and Comparative example : Self-luminous Photosensitive resin composition

A self-luminous photosensitive resin composition was prepared with the composition and contents shown in Table 1 below.

(Unit: parts by weight) Example 1 Example 2 Comparative Example 1 fluorescent dye A 4.64 4.64 4.64 Pigment B1 2.56 - - B2 - 2.56 - B3 - - 2.56 Alkali soluble resin C 23.03 23.03 23.03 Photopolymerizable compound D 15.74 15.74 15.74 Photopolymerization initiator E 0.4 0.4 0.4 menstruum F 53.63 53.63 53.63 A1: Lumogen F Red (manufactured by BASF)
B1: CI Pigment Yellow 138 (manufactured by BASF)
B2: CI Pigment Yellow 185 (manufactured by BASF)
B3: CI Pigment Red 254 (manufactured by BASF)
C: Alkali-soluble resin of manufacturing example 1
D: Dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
E: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)
F: Propylene glycol monomethyl ether acetate

Manufacturing example 2: Manufacturing of color filters

A color filter was manufactured using the self-luminous photosensitive resin compositions manufactured in the above Examples 1 to 2 and Comparative Example 1. That is, each of the self-luminous photosensitive resin compositions manufactured above was applied onto a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Next, ultraviolet rays were irradiated onto the thin film. At this time, an ultraviolet light source was used for irradiation at an exposure dose (365 nm) of 40 mJ/cm ² using an ultraviolet light source (product name: USH-250D) manufactured by Ushio Denki Co., Ltd. in an air atmosphere, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed in a KOH aqueous solution developing solution having a pH of 12.5 using a spray developer for 60 seconds, and then heated in a heating oven at 220° C. for 20 minutes to manufacture a color filter. The film thickness of the self-luminous color pattern manufactured above was 3.0 μm.

Experimental example : Luminescence intensity ( Intensity ) measurement

The luminescence (PL) of each coating substrate was measured using a quantum efficiency meter (QE-1000, manufactured by Otsuka Corporation) for the self-luminous color filter manufactured in the above Manufacturing Example 2, and the luminescence intensity is recorded in Table 2 below.

At this time, the higher the measured luminescence intensity, the better the luminance characteristics can be judged.

Luminescence intensity (maximum emission wavelength λ = 620 nm) Example 1 669 Example 2 660 Comparative Example 1 300

Referring to Table 2 above, it can be confirmed that in the case of the self-luminous photosensitive resin compositions (Examples 1 and 2) containing both the fluorescent dye and pigment of the present invention, the luminescence intensity is superior to that of the case containing a fluorescent dye or pigment outside the wavelength range of the present invention (Comparative Example 1).

10: Substrate
20: Color conversion layer
30: Color filter layer

Claims (8)

A self-luminous photosensitive resin composition comprising a fluorescent dye having an emission wavelength range of 520 to 700 nm; and a pigment having a maximum absorption wavelength range of 380 to 550 nm;
The above fluorescent dye comprises Lumogen F Red,
The above pigment includes CI Pigment Yellow,
A self-luminous photosensitive resin composition characterized in that the color filter including the cured product of the self-luminous photosensitive resin composition is used in combination with a light source that emits blue light. In the first paragraph,
A self-luminous photosensitive resin composition, characterized in that the self-luminous photosensitive resin composition further comprises at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. delete In the first paragraph,
A self-luminous photosensitive resin composition, characterized in that the fluorescent dye is contained in an amount of 0.1 to 70 wt% based on 100 wt% of the total self-luminous photosensitive resin composition containing the fluorescent dye. In the first paragraph,
A self-luminous photosensitive resin composition, characterized in that the pigment is included in an amount of 0.1 to 70 wt% based on 100 wt% of the total fluorescent dye included. In a color filter including a color conversion layer,
A color filter, characterized in that the color conversion layer comprises a cured product of the self-luminous photosensitive resin composition of any one of claims 1, 2, 4 and 5. An image display device including a color filter according to claim 6. In Article 7,
An image display device, characterized in that the image display device includes a light source.