KR20210106170A - Self emission type photosensitive resin composition, color filter comprising color conversion layer using the same and display device - Google Patents

Abstract

The present invention relates to a self-luminous photosensitive resin composition that includes: a colorant containing an aggregation-induced emission (AIE) green dye; an alkali-soluble resin; a photopolymerizable compounds; a photoinitiator; and a solvent, thereby providing excellent fluorescence efficiency to allow high color reproduction, and providing excellent reliability such as heat resistance or light resistance.

Description

Self-luminous photosensitive resin composition, color filter and image display device comprising a color conversion layer prepared therefrom

The present invention relates to a self-luminous photosensitive resin composition, a color filter including a color conversion layer prepared therefrom, and an image display device.

Recently, the display industry has undergone a rapid change from a cathode-ray tube (CRT) to a flat panel display represented by a plasma display panel (PDP), an organic light-emitting diode (OLED), and a liquid-crystal display (LCD). Among them, LCD is widely used as an image display device used in almost all industries, and its application range is continuously expanding.

In the LCD, the transmittance is adjusted as the white light generated from the backlight unit passes through the liquid crystal cell, and the three primary colors passing through the red, green, and blue color filters are mixed to realize full color.

A CCFL (Cold Cathode Fluorescent Lamp) is used as the light source of the backlight unit. In this case, power consumption is consumed because the backlight unit must always apply power to the CCFL. In addition, compared to the existing CRT, the color reproducibility of about 70% and environmental pollution problems due to the addition of mercury are pointed out as disadvantages.

As an alternative to solve the above problems, research on a backlight unit using a light emitting diode (LED) is being actively conducted. When an LED is used as a backlight unit, it can exceed 100% of the NTSC (National Television System Committee) color gamut specification to provide consumers with more vivid picture quality.

Accordingly, in the same industry, a method has been proposed by changing the material and structure of a color filter and an LCD panel in order to improve the efficiency of the backlight light source.

A color filter forms pixels of each color through a patterning process after applying a dispersion composition including a pigment or dye, and these pigments and dyes cause a problem of lowering the transmission efficiency of a backlight light source. As a result, the lowering of the transmission efficiency lowers the color reproducibility of the display device, which makes it difficult to realize a high-quality screen. Therefore, research to further improve the color reproducibility and optical characteristics is being conducted.

In this regard, Korean Patent Application Laid-Open No. 10-2017-0026245 discloses a novel phenylene-based compound and a fluorescent dye containing the same, but the high color reproducibility is not good and reliability is not good because the concentration quenching occurs at high concentration. there is a problem.

Republic of Korea Patent Publication No. 10-2017-0026245 (2017.03.08.) Republic of Korea Patent Publication No. 10-2010-0056437 (2010.05.27.)

The present invention is to solve the above problems, and it is possible to manufacture a color conversion layer, a color filter or an image display device capable of high color reproduction due to excellent fluorescence efficiency, and a self-luminous photosensitive resin having excellent reliability such as heat resistance or light resistance. It aims to provide a composition.

The self-luminous photosensitive resin composition of the present invention for achieving the above object includes: a colorant containing aggregation-inducing luminescent green dye; alkali-soluble resin; photopolymerizable compounds; photoinitiator; and solvents.

The color conversion layer of the present invention includes a cured product of the self-luminous photosensitive resin composition.

The color filter of the present invention includes the color conversion layer.

The image display apparatus of the present invention includes the color filter.

The self-luminous photosensitive resin composition of the present invention has advantages of excellent fluorescence efficiency and excellent reliability such as heat resistance or light resistance.

The color conversion layer of the present invention includes the cured product of the above-described self-luminous photosensitive resin composition, thereby having excellent color reproducibility and excellent reliability such as heat resistance or light resistance.

The color filter of the present invention has the advantage of excellent color reproducibility by including the above-described color conversion layer.

The image display device of the present invention has the advantage of excellent color reproducibility by including the above-described color filter.

1 illustrates a color filter including a color conversion layer according to an embodiment of the present invention.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in direct contact with another member but also a case in which another member is interposed between the two members.

In the present invention, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present invention, definitions known in the art for blue light, green light and red light may be used, for example, blue light means light having a wavelength selected from a wavelength of 400 nm to 500 nm, and green light is 500 nm. It means light having a wavelength selected from a wavelength of nm to 560 nm, and red light means light having a wavelength selected from a wavelength of 600 nm to 780 nm. Also, in the present invention, the green dye (fluorescent dye) absorbs at least a portion of blue light to emit green light.

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

< self-luminescence Photosensitive resin composition>

The self-luminous photosensitive resin composition according to an aspect of the present invention comprises: a colorant containing an Aggregation-Induced Emission (AIE) green dye; alkali-soluble resin; photopolymerizable compounds; photoinitiator; And by including a solvent, fluorescence efficiency is excellent, high color reproduction is possible, and there is an advantage of excellent reliability such as heat resistance or light resistance.

coloring agent

The self-luminous photosensitive resin composition according to one aspect of the present invention contains aggregation-inducing luminescent green dye.

The aggregation-inducing luminescent green dye may be a fluorescent dye. In this case, the fluorescent dye means a luminescent material emitting light of a unique wavelength by absorbing energy in the form of light or electricity from the outside. The fluorescent dye has a variety of emission spectra and excellent quantum efficiency compared to general dyes, and has advantages in terms of cost, and thus has high utility as a light conversion device. In particular, when realizing high-definition color display, it is advantageous to obtain a high converted light intensity by increasing the concentration of the color conversion material (eg, dye) to increase the absorbance of absorbed light in the color conversion layer, When the concentration of the color conversion material is increased in this way, the absorbed energy by the light emitted from the organic EL device repeats movement between the molecules of the color conversion material, and the color conversion material molecules are deactivated without light emission, concentration quenching A phenomenon called Therefore, in order to suppress such concentration quenching, it is necessary to dissolve or disperse the color conversion material in any medium to lower its concentration. can't get

The self-luminescence photosensitive resin composition according to an aspect of the present invention includes the aggregated emission-inducing green dye, wherein the aggregated emission-inducing green dye is characterized in that fluorescence is amplified in a state in which molecules are aggregated, such as in a film or solid state, High color reproduction is possible by suppressing the quenching phenomenon at high concentration, and there are advantages in reliability such as heat resistance or light resistance.

Although not limited thereto, the maximum emission wavelength region of the green dye may be 500 to 600 nm, preferably 510 to 560 nm. As such, when the emission wavelength region of the green dye is included in the above-described range, there is an advantage that the fluorescence efficiency can be further improved.

According to an embodiment of the present invention, the aggregation-inducing luminescent green dye may be a compound including a silol structure in its molecular structure, and in this case, there is an advantage that reliability such as heat resistance or light resistance can be further improved, and preferably The compound including the silol structure may be at least one selected from the group consisting of compounds represented by the following Chemical Formula 1, wherein each functional group described in the following Chemical Formula 1 may be substituted or unsubstituted.

[Formula 1]

(In Formula 1,

R ₁ and R ₂ are each independently a substituted or unsubstituted, C ₁ to C ₂₁ alkyl group, C ₆ to C ₂₆ aryl group or heteroaryl group,

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또는

이며,R _{3 To} R ₆ are each independently a substituted or unsubstituted, C _{6 To} C ₂₆ Aryl group, C _{6 To} C ₂₆ Heteroaryl group,

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or

is,

wherein R ₇ is each independently a substituted or unsubstituted, C ₁ to C ₁₀₀ alkyl group or C ₆ to C ₂₆ aryl group,

wherein n is an integer from 1 to 3, and m is an integer from 1 to 100).

In Formula 1, R ₁ and R ₂ may be preferably a C ₁ to C ₁₂ alkyl group, more preferably, the alkyl group may be a methyl group, and the aryl group may preferably be a C ₆ to C ₁₂ group. , more preferably a phenyl group.

_{The alkyl group of R 7} in Formula 1 may preferably be C ₁ to C ₂₁ , and more preferably C ₁ to C ₁₀ .

In Formula 1, m may be an integer of preferably 1 to 60, and more preferably an integer of 1 to 20.

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일 수 있고, 이들은 각각 치환 또는 비치환된 것일 수 있으며, 상기 화학식 1로 표시되는 화합물은 보다 구체적으로 하기 화학식 1-1 내지 1-19로 표시되는 화합물로 이루어진 군으로부터 선택되는 하나 이상일 수 있으며, 이 경우 형광효율은 물론 내열성 또는 내광성 등의 형광효율이 보다 향상될 수 있는 이점이 있다. According to an embodiment of the present invention, in Formula 1, R ₃ to R ₆ are each independently substituted or unsubstituted,

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may be, each of which may be substituted or unsubstituted, and the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1-1 to 1-19, more specifically, In this case, there is an advantage that fluorescence efficiency such as heat resistance or light resistance as well as fluorescence efficiency can be further improved.

(In Formulas 1-1 to 1-19, R ₁ and R ₂ are each independently methyl or phenyl.)

According to an embodiment of the present invention, the colorant may be included in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight based on the total weight of the self-luminous photosensitive resin composition. . When the content range of the colorant is included within the above range, fluorescence efficiency may be further improved, solubility in a solvent may be improved, which may be advantageous in terms of fairness, and reliability such as heat resistance or light resistance may be further improved. When the content range of the colorant exceeds the above range, aggregation of the fluorescent dye may occur and the fluorescence efficiency may rather decrease, and defects may appear on the surface during curing. have.

The self-luminous photosensitive resin composition of the present invention may further include a fluorescent dye, general pigment, or general dye other than the above-mentioned aggregation-inducing luminescent green dye within a range that does not impair the effect thereof, in which case the aggregation-inducing luminescent green dye Fluorescent dyes, general pigments, or general dyes other than those used in the art may be used without particular limitation.

Alkali-soluble resin

The self-luminous photosensitive resin composition according to one aspect of the present invention includes an alkali-soluble resin.

The alkali-soluble resin usually has reactivity and alkali solubility under the action of light or heat, and can act as a dispersing agent for the aforementioned colorant. In the present invention, the alkali-soluble resin acts as a binder resin for the aforementioned colorant. In addition, any resin soluble in the alkaline developer used in the developing step of the process for preparing the color conversion layer may be used without any particular limitation.

As for the said alkali-soluble resin, the copolymer etc. of a carboxyl group containing monomer and this monomer and other monomer copolymerizable are mentioned, for example. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule such as unsaturated tricarboxylic acids. have. Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), monophthalic acid (2-acryloyloxyethyl), and monophthalic acid (2-methacryloyloxyethyl). The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p- aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylic Rate, methoxypropylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide 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; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexyl maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. and macromonomers having These monomers can be used individually or in mixture of 2 or more types, respectively. In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, a monomer having a rosin skeleton, etc. are preferable because they tend to lower the specific dielectric constant. can

The acid value of the alkali-soluble resin is not particularly limited, but may be, for example, 20 to 200 mgKOH/g. When the acid value is within the above range, solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains at the time of development, so that the film remaining ratio can be improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution. In addition, the alkali-soluble resin has a polystyrene equivalent weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent) of 3,000 to 200,000, preferably may be 5,000 to 100,000. When the weight average molecular weight is within the above range, the hardness and the remaining film ratio of the cured product of the self-luminous photosensitive resin composition including the same may be improved, and the solubility of the non-exposed portion in the developer may be excellent, and thus the resolution may be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin may be 1.5 to 6.0, preferably 1.8 to 4.0, but is not limited thereto, and the molecular weight distribution is When included within the above-described range, developability may be improved.

The alkali-soluble resin may be included in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content in the self-luminous photosensitive resin composition. When the content of the alkali-soluble resin is included within the above range, the solubility in the developer is sufficient to suppress the occurrence of development residues on the substrate of the non-pixel portion, and the occurrence of film reduction in the pixel portion of the exposed portion during development It can be suppressed and there is an advantage that the omission property of the non-pixel portion can be improved. If the alkali-soluble resin is included in less than the above range, residues or pattern omissions may occur during the developing process, and if it exceeds the above range, it may not be easy to use as a photosensitive resin composition.

photopolymerizable compound

The self-luminous photosensitive resin composition according to an embodiment of the present invention includes a photopolymerizable compound.

The photopolymerizable compound refers to a compound that can be polymerized by the action of a photopolymerization initiator to be described later, and may include a monofunctional monomer, a bifunctional monomer, or other polyfunctional monomer, but the type of the photopolymerizable compound is not particularly limited in the present invention, Those used as a photopolymerizable compound in the art may be used without particular limitation.

The monofunctional monomer is, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N- vinylpi Rollidone etc. are mentioned.

The bifunctional monomer is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Said other polyfunctional monomer is, for example, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acryl a rate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

The above-mentioned monomers are not limited to those described above, and each of them may be used alone or in mixture of two or more, and among them, a polyfunctional monomer having a function of two or more may be preferably used.

The photopolymerizable compound may be included in an amount of 5 to 50 wt%, preferably 7 to 45 wt%, based on the total weight of the solid content in the self-luminous photosensitive resin composition. When the content of the photopolymerizable compound is included within the above range, the strength or smoothness of the color conversion layer formed therefrom may be improved.

photopolymerization initiator

The self-luminous photosensitive resin composition according to an aspect of the present invention includes a photopolymerization initiator.

The type of the photopolymerization initiator is not particularly limited in the present invention, and as long as it is used as a photopolymerization initiator in the art, it may be used without any particular limitation.

The photopolymerization initiator includes, for example, an acetophenone-based compound, a benzoin-based compound as an active radical generator, a benzophenone-based compound, a thioxanthone-based compound, a triazine-based compound, an acid generator, a sensitizer, etc. The argument may be preferably used, but is not limited thereto.

The acetophenone-based compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 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-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one of oligomers, etc., and preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

The benzophenone-based compound is, for example, benzophenone, o-benzoyl methyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (t -Butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'- di(N,N'- dimethylamino) benzophenone, etc. are mentioned.

The thioxanthone-based compound is, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxythioxanthone, etc. are mentioned.

The triazine-based compound may be used as an active radical generator for generating an active radical, but may also be used as an acid generator because it generates an acid together with the active radical. The triazine-based compound is, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2- Methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4 dimethoxyphenyl)ethenyl]-1,3,5-tri Ajin etc. are mentioned.

The active radical generator is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetraphenyl in addition to the compounds described above. -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like.

The acid generator is, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

The above-described photopolymerization initiator may be used alone or in combination of two or more.

The content of the photoinitiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the total weight of the alkali-soluble resin and the photopolymerizable compound included together. When the content of the photopolymerization initiator is included within the above range, the sensitivity of the self-luminous photosensitive resin composition including it is improved, so that the strength of the color conversion layer formed using the same, or the smoothness on the surface of the color conversion layer can be improved. have.

The self-luminous photosensitive resin composition of the present invention may further include a photopolymerization initiator adjuvant together with the above-described photopolymerization initiator, if necessary. The photopolymerization initiation adjuvant may be used to further promote polymerization of a photopolymerizable compound whose polymerization is initiated by a photoinitiator included therewith.

The type of the photopolymerization initiation adjuvant is not particularly limited in the present invention, and may be used without particular limitation as long as it is used as a photopolymerization initiation adjuvant in the art, for example, an amine compound, an alkoxyanthracene compound, a thioxanthone compound and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethyl benzoate. Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(di ethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone may be preferable.

Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene etc. are mentioned.

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone etc. are mentioned.

The above-mentioned photopolymerization initiation adjuvant may be used alone or in mixture of two or more, and may be purchased and used commercially.

As said commercially available photoinitiation adjuvant, a brand name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned, for example.

As such, when the photopolymerization initiator is further included, its content may be 10 moles or less, preferably 0.01 to 4 moles or less, per 1 mole of the photopolymerization initiator included together. When the photopolymerization initiation adjuvant is included in the above-described range, the sensitivity of the self-luminous photosensitive resin composition including the photopolymerization initiation adjuvant is further improved, and the productivity of the color conversion layer formed therethrough can be further improved.

solvent

The self-luminous photosensitive resin composition according to an embodiment of the present invention further comprises a solvent. The type of the solvent is not particularly limited in the present invention, and an organic solvent used as a solvent in the art may be used without any particular limitation.

The solvent is, for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl Ketones such as ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; ethyl 3-ethoxypropionate; Esters, such as methyl 3-methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C can be preferably used from the viewpoint of applicability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl, 3 -esters, such as methyl methoxypropionate, etc. are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate ethyl, 3-methoxy propionate methyl may be mentioned, but is not limited thereto. The above-mentioned solvents can be used individually or in mixture of 2 or more types.

The content of the solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on 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 with an application device such as a roll coater, a spin coater, a slat and spin coater, a slit coater (also referred to as a die coater), or an inkjet.

The self-luminous photosensitive resin composition of the present invention may further include an additive according to the user's needs in addition to the above-mentioned components.

additive

The type of the additive is determined as necessary and is not particularly limited in the present invention.

The additive may include, for example, a filler, another high molecular compound, a dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like.

The filler may include, for example, glass, silica, alumina, and the like.

The other high molecular compounds include, for example, curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. can be heard

As the dispersant, for example, commercially available surfactants can be used, and the surfactants include, for example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. In addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc., As trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (Dainippon Ink) Manufactured by Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Geneca Co., Ltd.) ), EFKA (manufactured by EFKA Chemicals), and PB 821 (manufactured by Ajinomoto Co., Ltd.).

The adhesion promoter is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

The ultraviolet absorber may specifically include, for example, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone, and the like.

The said aggregation inhibitor, sodium polyacrylate etc. are mentioned, for example.

The method for preparing the self-luminous photosensitive resin composition of the present invention can be prepared by a method commonly used in the art, and is not particularly limited in the present invention, but, for example, may be prepared by the following method.

The colorant containing the aggregation-inducing luminescent green dye of the present invention is dissolved in advance by mixing it with a solvent. At this time, if necessary, a part or all of the dispersant and the alkali-soluble resin may be blended together. A self-luminous photosensitive resin composition can be obtained by adding the remainder of the alkali-soluble resin, a photopolymerizable compound, and a photoinitiator to the dispersion thus obtained, and further adding an additive and an additional solvent to a predetermined concentration if necessary.

<Color conversion layer>

The color conversion layer according to another aspect of the present invention can reproduce high color by including the cured product of the self-luminous photosensitive resin composition, and has excellent reliability such as heat resistance or light resistance.

The cured product may be a photocured material cured by irradiating light to the self-luminous photosensitive resin composition, and in this case, a conventional method used in the art may be used for curing the photocured material. For example, a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp may be used to irradiate light to the entire surface of the coating film coated with the self-luminous photosensitive resin composition, laser light or a lens, a mirror, etc. It is also possible to irradiate the photocurable composition while scanning the converged light etc. obtained using In addition, when a mask having a light transmitting portion having a predetermined pattern is used, a light guide member formed by irradiating unconverged light to the composition through the mask or bundling a plurality of optical fibers may be used, and the optical fiber corresponding to the predetermined pattern in the light guide member A cured product can be formed by irradiating light through the photosensitive resin composition.

The thickness of the color conversion layer may be, for example, 0.5 μm to 500 μm, but is not limited thereto, and may be adjusted differently depending on the desired fluorescence efficiency.

<Color filter>

The color filter according to another aspect of the present invention has the advantage that high color reproduction is possible by including the color conversion layer.

1 illustrates a color filter according to an embodiment of the present invention, which will be described in more detail with reference to this.

The color filter may include the color conversion layer 20 on the light source 10 , and further include a substrate or a pattern layer 30 on the color conversion layer 20 . In this case, the substrate may be a substrate of the color conversion layer 20 itself, or may be any portion where the color conversion layer is located in a display device, etc., and is not particularly limited.

The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may include polyethersulfone (PES) or polycarbonate (PC), but is limited thereto. it's not going to be

The pattern layer 30 may be formed using a conventional photosensitive resin composition used in the art by a conventional method, for example, by applying the photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern. can be formed.

The pattern layer 30 may include, for example, a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. When light is irradiated, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

When the pattern layer 30 is applied to an image display device, the light emitted from the light source 10 is not particularly limited, but a light source emitting blue light may be used in terms of better color reproducibility.

The pattern layer 30 may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer 30 may further include a transparent pattern layer that does not contain quantum dot particles.

When only the pattern layer 30 of two colors is provided, a light source emitting light of a wavelength representing the remaining colors that is not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is to display blue color.

The color filter including the substrate and the pattern layer 30 as described above may further include a barrier rib formed between each pattern, and may further include a black matrix. In addition, a passivation layer formed on the pattern layer 30 of the color conversion layer 20 may be further included.

<Image display device>

An image display apparatus according to another aspect of the present invention includes the above-described color filter, so that high color reproduction is possible.

The image display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display for a digital camera and display devices such as a device and a display device for car navigation, and a color display device may be particularly suitable.

The image display device may include other components that can be included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention, but the present invention is not limited thereto. does not

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Synthesis Example: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g of vinyltoluene were prepared as a monomer dropping funnel. (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added, prepared by stirring and mixing, and 6 g of n-dodecanthiol as a chain transfer agent dropping tank , PGMEA 24g was put and stirred and mixed, was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dripping proceeded for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 3 hours, and then a gas introduction tube was introduced to mix oxygen/nitrogen = 5/95 (v/v). Bubbling of gas was started. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added into the flask, and the reaction was continued at 110° C. for 8 hours to obtain a resin having a solid content acid value of 70 mgKOH/g. The polystyrene equivalent weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3. At this time, the GPC measurement conditions were as follows.

[GPC measurement conditions]

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

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

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

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

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw/Mn).

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

A self-luminous photosensitive resin composition was prepared by mixing each of the components shown in Table 1 according to the contents described below.

(Unit: % by weight) Example comparative example One 2 3 4 5 6 7 8 9 10 11 One 2 3 fluorescent dye dye 1 - - - - - - - - - - - One - - dye 2 - - - - - - - - - - - - One - dye 3 - - - - - - - - - - - - - One dye 4 One - - - - 0.05 0.3 13 18 22 32 - - - dye 5 - One - - - - - - - - - - - - dye 6 - - One - - - - - - - - - - - dye 7 - - - One - - - - - - - - - - dye 8 - - - - One - - - - - - - - - Alkali-soluble resin (B) 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 Photopolymerizable compound (C) 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 photopolymerization initiator
(D) D-1 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 D-2 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Solvent (E) remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount Dye 1: pyrrole-based green fluorescent dye (bodipy)
Dye 2: Pyrenic green dye (pyranine)
Dye 3: Xanthenic green dye (fluorescein)
Dye 4: Aggregation-inducing luminescent green dye of Formula 1-1
Dye 5: Aggregation-inducing luminescent green dye of Formula 1-2
Dye 6: Aggregation-inducing luminescent green dye of Formula 1-3
Dye 7: Aggregation-inducing luminescent green dye of Formula 1-4
Dye 8: aggregation-inducing luminescent green dye of formula 1-5
B: Alkali-soluble resin of the synthesis example
C: dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.)
D-1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one
(Irgacure 369; manufactured by Ciba Specialty Chemical)
D-2: 4,4'-di(N,N'-dimethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
E: propylene glycol monomethyl ether acetate

manufacturing example : color conversion layer Produce

A color conversion layer was prepared using the self-luminous photosensitive resin composition prepared in each of Examples and Comparative Examples. That is, each of the self-luminous photosensitive resin compositions was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. at an exposure dose (365 nm) of 40 mJ/cm 2 in an atmospheric atmosphere, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed in a KOH aqueous solution developing solution having a pH of 12.5 for 60 seconds using a spray developer, and then heated in a heating oven at 230° C. for 20 minutes to prepare a pattern. The film thickness of the color conversion layer pattern prepared above was 3.0㎛.

Experimental example 1: Luminescence intensity ( Intensity ) measurement

For each color conversion layer prepared in Preparation Example, using a quantum efficiency meter (QE-1000, manufactured by Otsuka Co., Ltd.), the light emission intensity for each color conversion layer was measured, and the results are shown in Table 2 below. did. In this case, it can be determined that the higher the measured light emission intensity, the better the luminance characteristic.

Experimental example 2. Heat resistance evaluation

In the evaluation of the heat resistance of each color conversion layer prepared in Preparation Example, the color change before and after heating at 230 ° C. for 120 minutes was comparatively evaluated, and the results are described in Table 2 below. It is judged that the higher the temperature, the better the heat resistance. In this case, the following Equation 1 is used to represent the color change in a three-dimensional colorimeter defined by L*, a*, and b*. 266).

[Equation 1]

ΔEab={(ΔL*) ² +(Δa*) ² +(Δb*) ² } ^{1 /2}

<Evaluation criteria>

○: △Eab is less than 2

×: ΔEab is 2 or more

Experimental example 3. light fastness evaluation

An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Corporation; blocks light of 380 nm or less) is placed on each color conversion layer prepared in the above preparation example, and a light resistance tester (Santest CPS+: manufactured by Toyo Seiki Co., Ltd.) ) and irradiated with xenon lamp light for 48 hours. The color change before and after irradiation was comparatively evaluated, and the results are shown in Table 2 below, and it is judged that the smaller the color change value, the better the light resistance. The equations and evaluation criteria used at this time were performed in the same manner as in the heat resistance evaluation.

Luminescence intensity (λmax: 550) Heat resistance evaluation Light fastness evaluation Example 1 4800 ○ ○ Example 2 4650 ○ ○ Example 3 4700 ○ ○ Example 4 4500 ○ ○ Example 5 4550 ○ ○ Example 6 3900 ○ ○ Example 7 4100 ○ ○ Example 8 4350 ○ ○ Example 9 4200 ○ ○ Example 10 4000 ○ ○ Example 11 3800 ○ ○ Comparative Example 1 2800 ○ ○ Comparative Example 2 3100 × × Comparative Example 3 2600 × ×

Referring to Table 2, when all of the components presented in the present invention are included (Examples 1 to 11), the luminescence intensity is higher than when none of the components presented in the present invention are included (Comparative Examples 1 to 3). was excellent, and it was confirmed that the reliability such as heat resistance and light resistance was excellent.

10: light source
20: color conversion layer
30: pattern layer

Claims (9)

a colorant containing agglutination-inducing luminescent green dye; alkali-soluble resin; photopolymerizable compounds; photoinitiator; And a self-luminous photosensitive resin composition comprising a solvent. According to claim 1,
The aggregation-inducing luminescent green dye is a self-luminous photosensitive resin composition, characterized in that it is a compound including a silol structure in its molecular structure. 3. The method of claim 2,
The self-luminous photosensitive resin composition, characterized in that the compound including the silol structure is a compound represented by the following formula (1).
[Formula 1]

(In Formula 1,
R ₁ and R ₂ are each independently a substituted or unsubstituted, C ₁ to C ₂₁ alkyl group, C ₆ to C ₂₆ aryl group or heteroaryl group,
R _{3 To} R ₆ are each independently a substituted or unsubstituted, C _{6 To} C ₂₆ Aryl group, C _{6 To} C ₂₆ Heteroaryl group,

,

or

is,
wherein R ₇ is each independently a substituted or unsubstituted, C ₁ to C ₁₀₀ alkyl group or C ₆ to C ₂₆ aryl group,
wherein n is an integer from 1 to 3, and m is an integer from 1 to 100). 4. The method of claim 3,
The R _{3 To} R ₆ are each independently substituted or unsubstituted,

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or

A self-luminous photosensitive resin composition, characterized in that 4. The method of claim 3,
The compound represented by Formula 1 is a self-luminous photosensitive resin composition, characterized in that at least one selected from the group consisting of compounds represented by Formulas 1-1 to 1-19.

(In Formulas 1-1 to 1-19, R ₁ and R ₂ are each independently methyl or phenyl.) According to claim 1,
The colorant is a self-luminous photosensitive resin composition, characterized in that it is included in an amount of 0.01 to 30% by weight based on the total weight of the self-luminous photosensitive resin composition including the colorant. A color conversion layer comprising a cured product of the self-luminous photosensitive resin composition of any one of claims 1 to 6. A color filter comprising the color conversion layer of claim 7. An image display device comprising the color filter of claim 8 .

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