KR20210115839A - A photosensitive resin composition for forming partition wall, a partition wall structure prepared using the composition, and a display device comprising the partition wall structure - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a barrier rib, including an alkali-soluble resin, a polymerizable compound, a photoinitiator and a solvent. Provided are a photosensitive resin composition for forming a barrier rib, a barrier rib structure for a display device manufactured using the photosensitive resin composition, and a display device including the same, wherein a cured film manufactured using the photosensitive resin composition has a transmittance of less than 5% at a wavelength of 450 nm and a reflectance of 30% or more at a wavelength of 640 nm when the cured film has a thickness of 7 to 15 μm.

Description

A photosensitive resin composition for forming a barrier rib, a barrier rib structure manufactured using the same, and a display device including the barrier rib structure TECHNICAL FIELD STRUCTURE}

The present invention relates to a photosensitive resin composition for forming barrier ribs, a barrier rib structure manufactured using the same, and a display device including the barrier rib structure.

In general, a display device including a color conversion panel using a blue light source exhibits light blocking characteristics with respect to blue used as a light source, and a partition is formed between each color conversion pixel to prevent color mixing of each color conversion pixel. Due to the conversion efficiency of the conversion pixel, the partition wall between each color conversion pixel is formed with a film thickness of about 7 mu m to 15 mu m.

When the conventionally used photosensitive resin composition for a black matrix has a film thickness of 1 µm to 1.5 µm, there is no problem in pattern formation. However, the barrier rib for the color conversion panel should have a film thickness of 7 μm to 15 μm. When the barrier rib is formed with a thick film using the conventional black matrix, the line width of the pattern is greatly changed according to the development time in the developing process due to the decrease in the transmittance of ultraviolet rays in the exposure process. When the line width of the barrier rib between the color conversion pixels is increased in the same area, the size of the color conversion pixel is reduced, so that there is a problem in that the color conversion performance of the color conversion panel is lowered.

In addition, when manufacturing a partition wall for a color conversion panel, if a conventional photosensitive resin composition for a black matrix is used, it is difficult to recognize the lower Align key when aligning the mask pattern in the exposure process after the coating process, so that the pattern is formed at the correct position There is a problem that it is difficult to do. Furthermore, in the barrier rib formed using the conventional photosensitive resin composition for a black matrix, light scattered by the barrier rib among the red or green light scattered by quantum dots is absorbed by the barrier rib and disappears, so the luminous efficiency of the color conversion panel is lowered. There is this.

Meanwhile, in the prior art, a coloring pattern using an organic pigment is prepared in order to manufacture a color filter. In this case, in order to represent each desired color, the C.I. Red pigment (C.I. Pigment Red) to C.I. C.I. Pigment Orange, and C.I. Pigment Orange for patterns that want green. Green pigment (C.I. Pigment Green) to C.I. Yellow pigment (C.I. Pigment Yellow) is used together. Since the thickness of the color filter coating film is usually manufactured to be 2 μm to 3 μm, it is different from the above-described technology for manufacturing a partition wall for a color conversion panel having a thickness of 7 μm to 15 μm. The purpose of the filter is to represent a specific color on color coordinates, and characteristics such as luminance and contrast are important, whereas the partition wall for a color conversion panel is a display device technology manufactured by a combination of a display including a color conversion panel and a blue light source. has a difference in

In relation to this, Korean Patent Application Laid-Open No. 10-2007-0094460 aims to provide a photosensitive resin composition for forming a barrier rib having excellent shape stability against heat, but the above-described problem cannot be overcome.

Republic of Korea Patent Publication No. 10-2007-0094460

The present invention is to improve the above-described prior art problems, to provide a photosensitive resin composition for forming a barrier rib that can efficiently block blue-based light and improve color conversion characteristics for red and green-based light The purpose.

Another object of the present invention is to provide a photosensitive resin composition for forming a barrier rib having a small change in the line width of the pattern according to the development time in the developing process.

Another object of the present invention is to provide a structure manufactured using the photosensitive resin composition for forming barrier ribs and a display device including the barrier rib structure.

The present invention is a photosensitive resin composition for forming a barrier rib comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the cured film prepared from the photosensitive resin composition has a thickness of 7 μm to 15 μm, and a wavelength of 450 nm The transmittance is less than 5%, and the reflectance at a wavelength of 640 nm is 30% or more, to provide a photosensitive resin composition for forming barrier ribs.

In addition, the present invention provides a barrier rib structure for a color conversion pixel made of the photosensitive resin composition.

In addition, the present invention provides a display device including a color conversion panel including the barrier rib structure for the color conversion pixel.

The cured film prepared by using the photosensitive resin composition for forming a barrier rib of the present invention has a transmittance of less than 5% at a wavelength of 450 nm and a reflectance of 30% or more at a wavelength of 640 nm when the thickness of the cured film is 7 μm to 15 μm. By doing so, it is possible to efficiently block blue-based light and at the same time increase reflectance for red and green-based light, thereby providing an effect of improving the color conversion characteristics of a color conversion panel including the same.

In addition, the photosensitive resin composition of the present invention can form a structure with a small change in pattern line width according to the change in the development time in the developing process, thereby forming a color conversion pixel of a certain size, so that the size of the color conversion pixel is reduced It provides an effect that can prevent the color conversion performance from being reduced.

In addition, the barrier rib structure manufactured using the photosensitive resin composition of the present invention can be effectively applied to a color conversion panel using a blue light source and a display device including the same, thereby providing a high-quality display device.

1 is a view showing the transmission spectrum of a cured film prepared by using the photosensitive resin composition according to Example 3, Example 6, and Comparative Example 5 of the present invention.
2 is a view showing the reflection spectrum of a cured film prepared by using the photosensitive resin composition according to Example 3, Example 6, and Comparative Example 5 of the present invention.

The present invention is a photosensitive resin composition for forming a barrier rib comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the cured film prepared from the photosensitive resin composition has a thickness of 7 μm to 15 μm, and a wavelength of 450 nm Provided are a photosensitive resin composition for forming barrier ribs, a barrier rib structure made of the photosensitive resin composition, and a display device including the same, wherein the transmittance is less than 5% and the reflectance is 30% or more at a wavelength of 640 nm.

When the cured film made of the photosensitive resin composition has a thickness of 7 μm to 15 μm, the maximum transmittance at a wavelength of 450 nm may be preferably less than 4%, and more preferably less than 3%.

In addition, when the cured film made of the photosensitive resin composition has a thickness of 7 μm to 15 μm, the reflectance at a wavelength of 640 nm may be preferably 33% or more, and more preferably 36% or more.

In addition, the cured film prepared from the photosensitive resin composition, when the thickness of the cured film is 7㎛ to 15㎛, may have a reflectance of 30% or more at a wavelength of 550nm, preferably 35% or more, more preferably 40% may be more than

When the cured film satisfies the specific transmittance and specific reflectance conditions at the specific wavelength described above, it is possible to efficiently block blue-based light used as a light source from the rear side, and efficiently reflect red and green-based light. , may exhibit excellent light blocking properties and color conversion properties in a display device using a blue light source including the cured film as a barrier rib structure.

A display device including a color conversion panel implements an image by converting blue (high energy) light into green (low energy) or red (low energy) light by using quantum dots for color conversion pixels. The barrier rib structure used has a very important technical purpose in terms of preventing inter-pixel interference of the blue light source used as the light source, thereby preventing the mixing of blue, green, and red pixels generated in each pixel. There is a technical difference from a barrier rib structure used in a color filter that transmits light of a specific wavelength to realize a color.

Meanwhile, in a display device including a color conversion panel, the thickness of each color conversion pixel is formed to be about 10 μm thick in order to increase the absorbance of the color conversion layer and obtain sufficient light conversion efficiency. Accordingly, the barrier rib structure for the color conversion panel needs to be formed to a thickness of 7 μm to 15 μm depending on the thickness of the color conversion pixel.

In addition, the barrier rib structure according to the prior art is generally formed in black, but at a film thickness of 7 µm to 15 µm instead of the commonly used film thickness of 1 µm to 2 µm, the film thickness is too thick in the exposure process, so that the ultraviolet transmittance is low. Because it is lowered, photocuring cannot be induced to the depths. If the deep part of the coating film is not photocured, there is a problem in that the line width of the pattern changes depending on the development time in the developing process, or in severe cases, the pattern is lost because the lower part of the pattern is all developed. Therefore, there is a limit to using a black photosensitive resin composition, such as a conventional photosensitive resin composition for a black matrix, as a material for forming a barrier rib structure.

The photosensitive resin composition according to the present invention can form a red, yellow, or orange-based barrier rib structure, and can induce sufficient photocuring to a deep part even when a cured film having a film thickness of 7 μm to 15 μm is formed. It has the advantage of being able to provide a barrier rib structure with a small change in the line width of the pattern according to the change in the development time. In this case, the line width of the pattern may be formed in a range of 10 μm to 50 μm.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition for forming a barrier rib according to the present invention includes an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and may further include at least one selected from a colorant and scattering particles.

The photosensitive resin composition according to the present invention may be characterized in that it is for forming a partition wall of a color conversion panel using a blue light source.

Alkali-soluble resin

The alkali-soluble resin has reactivity and alkali solubility under the action of light or heat, acts as a dispersion medium of the solid contained in the photosensitive resin composition, and if it performs the function of a binder resin, a resin known in the art is selected without particular limitation can be used by

Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

As said unsaturated carboxyl group-containing monomer, the unsaturated carboxylic acid etc. which have one or more carboxyl groups in a molecule|numerator, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and an unsaturated polyhydric carboxylic acid, are mentioned, for example.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

As said unsaturated dicarboxylic acid, maleic acid, a fumaric acid, itaconic acid, a citraconic acid, mesaconic acid etc. are mentioned, for example.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the said unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, For example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both terminals, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. .

The unsaturated carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the other monomer copolymerizable with the unsaturated carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m- Methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p -Aromatic vinyl compounds, such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-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, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadie Nyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate unsaturated carboxylic acid esters such as; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl 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; unsaturated imides such as maleimide, N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or a 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. macromonomers and the like. These monomers can be used individually or in mixture of 2 or more types, respectively.

The content of the alkali-soluble resin may be included in an amount of 20 to 70% by weight, preferably 30 to 60% by weight, based on the total weight of the solid content in the photosensitive resin composition. When the alkali-soluble resin is included within the above range, it is preferable because the solubility in the developer is sufficient to facilitate the formation of a cured film, and the film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission property of the unexposed portion is improved. .

In the present invention, the total weight of the solid content in the photosensitive resin composition means the total weight of the remaining components excluding the solvent of the photosensitive resin composition.

polymeric compound

The polymerizable compound is a compound that can be polymerized by light and heat, and as long as it can be polymerized by light and heat, a polymerizable compound known in the art can be selected and used without particular limitation, and specifically, a monofunctional monomer, A bifunctional monomer, another polyfunctional monomer, etc. can be used.

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxyethyl acryl Late, N-vinylpyrrolidone, etc. are mentioned.

The type of the bifunctional monomer is not particularly limited, and 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, etc. are mentioned.

The type of the polyfunctional monomer is not particularly limited, and for example, 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, etc. are mentioned.

Commercially available examples of the polymerizable compound include, but are not limited to, Miramer M600 manufactured by Miwon Corporation.

The content of the polymerizable compound may be included in an amount of 5 to 50 wt%, preferably 10 to 40 wt%, based on the total weight of the solid content in the photosensitive resin composition. When the polymerizable compound is included within the above range, it is preferable in terms of strength or smoothness of the pixel portion.

photopolymerization initiator

As the photopolymerization initiator, a photopolymerization initiator known in the art may be selected and used without particular limitation. For example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds and the like may be used.

For example, as the oxime-based compound, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one may be used, and commercial products include OXE-01 and OXE-02 manufactured by Ciba Corporation. , but is not limited thereto.

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

The content of the photopolymerization initiator may be 0.01 to 10 wt%, preferably 0.01 to 5 wt%, based on the total weight of the solid content in the photosensitive resin composition. When the photopolymerization initiator is included within the above range, the photopolymerization reaction rate is appropriate to prevent an increase in the overall process time, and it is preferable to prevent deterioration of physical properties of the final cured film due to overreaction.

The photosensitive resin composition according to the present invention may further include a photopolymerization initiator auxiliary in addition to the photopolymerization initiator. When a photopolymerization initiation auxiliary is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and productivity is improved.

The photopolymerization initiation adjuvant is a compound used to promote polymerization of a polymerizable compound whose polymerization is initiated by the photoinitiator, and at least one compound selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

When the photopolymerization initiation aid is included, its content may be typically greater than 0 moles to 10 moles or less, preferably 0.01 moles to 5 moles, based on 1 mole of the photopolymerization initiator. When the photopolymerization initiation adjuvant is included within the above range, it is preferable because the effect of improving the productivity can be expected by improving the photopolymerization efficiency.

solvent

As the solvent, an organic solvent known in the art may be used without particular limitation.

Specific examples of the solvent include 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, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, Esters, such as methyl 3-methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

The solvent may use an organic solvent having a boiling point of preferably 100°C to 200°C in terms of applicability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl, 3 -Esters such as methyl methoxypropionate can be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, etc. can be used

Each of the above solvents may be used alone or in combination of two or more.

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 photosensitive resin composition. When the solvent is contained within the above content range, the effect of improving the applicability when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable to provide

coloring agent

The photosensitive resin composition according to the present invention may include a colorant.

The colorant is C.I. Red pigment (C.I. Pigment Red), C.I. C.I. Pigment Yellow and C.I. It is preferable to include at least one selected from the group consisting of an orange pigment (C.I. Pigment Orange), and accordingly, the photosensitive resin composition according to the present invention may form a red, yellow or orange-based partition structure. The red, yellow, or orange-based barrier rib structure formed as described above absorbs blue-based light and reflects red and/or green-based light to prevent mixing of blue light in a display device using a blue light source, and / or it is possible to improve the light emitting characteristic of the green series.

Preferably, the C.I. The red pigment (C.I. Pigment Red) may be at least one selected from diketopyrrole-based, anthraquinone-based, perylene-based and azo-based, and the C.I. The yellow pigment (C.I. Pigment Yellow) may be at least one selected from anthraquinone-based, isoindolinone-based, and azo-based pigments, and the C.I. Orange pigment (C.I. Pigment Orange) may be at least one selected from quinophthalone-based, isoindolinone-based, and diketopyrrole-based.

More preferably, the C.I. The red pigment is C.I. red pigment 9, 81, 97, 105, 122, 123, 144, 149, 150, 155, 166, 168, 171, 175, 176, 177, 179, 180, 185, 192, 202, 208, 209, 214, It may be at least one selected from the group consisting of 215, 216, 220, 222, 224, 242, 254, 255, 264, 269, 270 and 272,

The C.I. Yellow pigments, C.I. Yellow pigment 11, 13, 20, 24, 31, 53, 83, 86, 93, 94, 95, 99, 108, 109, 110, 117, 125, 128, 129, 138, 139, 147, 148, 150, It may be at least one selected from the group consisting of 151, 154, 155, 166, 167, 173, 180, 185 and 199,

The C.I. Orange pigment is C.I. The orange pigment may be at least one selected from the group consisting of 13, 15, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71.

Most preferably, the C.I. The red pigment is C.I. It is at least one selected from the group consisting of red pigments 177, 179, 254, 264 and 269, and the C.I. The yellow pigment is C.I. It is at least one selected from the group consisting of yellow pigments 138, 139, 150 and 185, and the C.I. Orange pigment is C.I. It may be at least one selected from the group consisting of orange pigments 64 and 71.

In addition, the present invention has a feature that can effectively block blue-based light without including a black colorant. Accordingly, the colorant of the present invention preferably does not include a black colorant. However, if necessary, it may contain up to 10% by weight, more preferably up to 5% by weight, based on the total weight of the colorant. If the black colorant is included in an excessive amount as a colorant, reverse taper may occur due to insufficient hardening of the deep part, and there is a problem in that the luminous efficiency of the display device is deteriorated due to a decrease in reflectance, which is not preferable.

Specifically, the black colorant may include black organic/inorganic pigments and dyes such as carbon black, titanium black, aniline black, lactam black, and perylene black, and even a combination capable of representing black by including a plurality of colorants can be understood as a concept.

When the photosensitive resin composition for forming a barrier rib according to the present invention includes the colorant, the content thereof may be 1 to 30 wt%, preferably 1.5 to 25 wt%, based on the total weight of the solid content in the photosensitive resin composition. When the colorant is included within the above range, light blocking characteristics for blue light may be improved, and reflectance with respect to red and/or green light may be increased to improve light emitting characteristics of the display device.

Meanwhile, as the pigment, a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed may be used. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant is added for deagglomeration and stability maintenance of the pigment, and those generally used in the art may be used without limitation, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, Surfactants, such as polyester type and polyamine type, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA), and other resin types in addition to the acrylate-based dispersant. of pigment dispersant can also be used. The resin-type pigment dispersant may be used alone or in a mixture of two or more, or may be used in combination with the acrylate-based dispersant.

scattering particles

The photosensitive resin composition for forming barrier ribs according to the present invention may include scattering particles.

The scattering particles may be used by selecting scattering particles known in the art without particular limitation. Specifically, the scattering particles are Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y , Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr , Nb, Ce, Ta, In, and may include one or more oxides selected from the group consisting of combinations thereof. For example, the scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , may include at least one selected from the group consisting of SnO and MgO, and if necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

As for the scattering particles, those having an average particle diameter and a limited content in the entire composition may be used to maximize the emission intensity of the color filter.

In the present invention, the "average particle diameter" may be a number average particle diameter, for example, it can be obtained from an image observed by a field emission principal electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, it is possible to obtain a value obtained by extracting several samples from an observation image of FE-SEM or TEM, measuring the diameters of these samples, and arithmetic average.

For example, the scattering particles of the present invention may have an average particle diameter of 30 to 500 nm, preferably 30 to 300 nm. When the average particle diameter of the scattering particles satisfies the above range, the scattering effect is increased, so that the photosensitive resin composition including the scattering particles can easily secure reflectance for red and/or green light.

When the photosensitive resin composition for forming barrier ribs according to the present invention includes the scattering particles, the content thereof may be 0.1 to 50% by weight, preferably 0.5 to 20% by weight based on the total weight of solids in the photosensitive resin composition. When the scattering particles are included within the above range, it is preferable because it is easy to secure reflectance for red and/or green-based light, and it is possible to suppress a decrease in stability of the composition.

additive

The photosensitive resin composition according to the present invention may further include an additive as necessary, and the type of the additive may be determined according to the needs of the user and is not particularly limited in the present invention, but, for example, a filler, other A high molecular compound, a thermosetting agent, surfactant, an adhesion promoter, antioxidant, aggregation inhibitor, a dispersing agent, etc. are mentioned. The additives exemplified above may be used alone or in combination of two or more.

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane; and the like.

The antioxidant may include, for example, at least one selected from the group consisting of phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants, and in this case, a color change phenomenon that may occur at high temperatures during the process or a light source after display manufacturing It can inhibit the occurrence of yellowing that can be caused by The antioxidant may include at least one selected from the group consisting of a phenolic compound, a phosphorus compound, and a sulfur compound, which are a phenolic-phosphorus compound, a phenolic-sulfur compound, a phosphorus-sulfur compound, or a phenolic-phosphorus compound. -Can be used in combination with sulfur compounds.

The content of the antioxidant may be 0.1 to 30% by weight, preferably 0.5 to 20% by weight based on the total weight of the solid content in the photosensitive resin composition. When the antioxidant is included within the above range, it is preferable in terms of solving the problem of lowering the luminescence intensity.

The dispersing agent is added to maintain dispersion stability of the pigment, and those generally used in the art may be used without limitation.

In the case of additives whose content is not exemplified among the above additives, those skilled in the art may appropriately add and use the additives within a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, more preferably 0.1 to 5 wt%, based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition of the present invention may be prepared by a conventional method known in the art, and is not particularly limited in the present invention, but may be prepared by, for example, the following method.

The colorant and/or the scattering particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the colorant has an average particle diameter of 30 to 300 nm. At this time, a dispersing agent may be additionally used if necessary, and some or all of the alkali-soluble resin may be blended. To the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the alkali-soluble resin, a polymerizable compound and a photoinitiator, additional additives as necessary, and additional solvents as necessary are further added to a predetermined concentration, The desired photosensitive resin composition can be obtained.

<Bulkhead structure and display device>

The present invention provides a barrier rib structure made of the photosensitive resin composition and a display device including the same.

In a display device including a color conversion panel, since each pixel is driven to form a color, a barrier rib structure capable of distinguishing each pixel from each other is required. A display device including a barrier rib structure for a color conversion panel formed by using the photosensitive resin composition of the present invention prevents color mixing between pixels, is advantageous for forming a fine pattern, and has little line width change due to a change in development time in the developing process. It is possible to manufacture bulkheads. When the change in the line width of the barrier rib is small, the color conversion pixel can secure sufficient space and has the advantage of realizing a high-quality image.

The display device may include a liquid crystal display device, an organic light emitting diode, a flexible display, and the like, but is not limited thereto, and all display devices known in this field that can be applied may be exemplified.

The barrier rib structure including a color conversion panel can be manufactured by applying the photosensitive resin composition of the present invention described above on a substrate, photocuring and developing to form a cured film.

First, after apply|coating a photosensitive resin composition on a base material, volatile components, such as a solvent, are removed by heat-drying, and a smooth coating film is obtained.

As a coating method, it can carry out, for example by the spin coating method, the cast coating method, the roll coating method, the slit-and-spin coating method, or the slit coating method. After application, heat drying (pre-baking), or drying under reduced pressure is heated to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 150°C, and preferably 80 to 130°C. The thickness of the coating film after heat drying is usually about 7 to 15 µm. In this way, the obtained coating film is irradiated with an ultraviolet-ray through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are accurately aligned. When ultraviolet rays are irradiated, radicals are formed by the photopolymerization initiator at the site irradiated with ultraviolet rays, and photocuring occurs by reacting with the polymerizable compound.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. may be used. The irradiation amount of ultraviolet rays may be appropriately selected according to need, and the present invention is not limited thereto. When the photocured coating film is brought into contact with a developer to dissolve the unexposed portion and developed, the desired pattern shape can be obtained.

The pattern shape thus obtained can be made hard through a post-curing process, and the heating temperature is usually 150 to 250°C, and preferably 180 to 230°C. The heating time is usually 5 to 30 minutes, preferably 15 to 20 minutes.

Hereinafter, although this invention is demonstrated in more detail based on an Example, embodiment of this invention disclosed below is only an illustration to the last, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it embraces all modifications within the meaning and scope equivalent to those recorded in the claims. In addition, in the following Examples and Comparative Examples, "%" and "part" indicating the content are based on mass unless otherwise specified.

<Example>

Synthesis Example 1: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, while 15 parts by weight of N-benzylmaleimide, 30 parts by weight of acrylic acid, 50 parts by weight of cyclohexyl methacrylate, and methyl methacrylate 5 parts by weight, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA) were added, stirred and mixed to prepare a monomer dropping lot, and n- 6 parts by weight of dodecanediol and 24 parts by weight of PGMEA were added and mixed with stirring to prepare a chain transfer agent dropping lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was substituted from air to nitrogen, 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 dropping was carried out for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours. Bubbling was started.

Then, 20 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were added into the flask, and the flask was heated at 110° C. for 6 hours. The reaction was continued, and thereafter, while cooling to room temperature, alkali-soluble resin having a weight average molecular weight of 3,800 and an acid value based on solid content of 83 mgKOH/g was obtained.

The weight average molecular weight (Mw) of the alkali-soluble resin was measured by GPC method, and HLC-8120GPC (manufactured by Tosoh Corporation) was used.

Measurement conditions were used by connecting TSK-GELG4000HXL and TSK-GELG2000HXL columns in series, and the temperature of the column was set to 40°C. Tetrahydrofuran was used as a mobile phase solvent, and it was measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 μl, and it was analyzed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material for calibration, and the weight average molecular weight of the alkali-soluble resin obtained under the above conditions was measured. did.

Examples 1 to 11 and Comparative Examples 1 to 7: Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were prepared according to the composition and content of Table 1 below.

(Unit: % by weight) Example comparative example One 2 3 4 5 6 7 8 9 10 11 One 2 3 4 5 6 7 coloring agent R177 1.75 - - - - - - - - - - - - - - - - - R179 - 1.75 - - - - - - - - - 1.75 - - - - - - R254 - - 1.75 - - - - - - - - - - - - - - - R264 - - - 1.75 - - - - - - - - - - - - - - R269 - - - - 1.75 - - - - - - - - - - - - - Y138 - - - - - 1.75 - - - - - - - - - - - - Y139 - - - - - - 1.75 - - - - - - - - - - - Y150 - - - - - - - 1.75 - - - - 1.75 - - - - - Y185 - - - - - - - - 1.75 - - - - - - - - - O64 - - - - - - - - - 1.75 - - - - - - - - O71 - - - - - - - - - - 1.75 - - - - - - - B7 - - - - - - - - - - - - - - 1.75 - - - OB - - - - - - - - - - - - - - - 1.75 - - G36 - - - - - - - - - - - - - - - - 1.75 - B15:6 - - - - - - - - - - - - - - - - - 1.75 scattering particles 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 - - 1.25 1.25 1.25 1.25 1.25 Alkali-soluble resin 13.40 13.40 13.40 13.40 13.40 13.40 13.40 13.40 13.40 13.40 13.40 14.27 14.27 14.61 13.40 13.40 13.40 13.40 photopolymerizable compound 7.22 7.22 7.22 7.22 7.22 7.22 7.22 7.22 7.22 7.22 7.22 7.68 7.68 7.87 7.22 7.22 7.22 7.22 photopolymerization initiator 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.10 1.10 1.12 1.03 1.03 1.03 1.03 dispersant 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.20 0.20 0.15 0.35 0.35 0.35 0.35 solvent 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00

- R177: C.I. red pigment 177

- R179: C.I. red pigment 179

- R254: C.I. red pigment 254

- R264: C.I. red pigment 264

- R269: C.I. red pigment 269

- Y138: C.I. yellow pigment 138

- Y139: C.I. yellow pigment 139

- Y150: C.I. yellow pigment 150

- Y185: C.I. yellow pigment 185

- O64: C.I. Orange Pigment 64

- O71: C.I. Orange Pigment 71

- B7: C.I. black pigment 7

- OB: organic black pigment

- G36: C.I. green pigment 36

- B15:6: C.I. Blue Pigment 15:6

- Scattering particles: TiO ₂

- Alkali-soluble resin: alkali-soluble resin according to Synthesis Example 1

- Photopolymerizable compound: dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Chemicals)

- Photoinitiator: Irgacure OXE-02 (manufactured by Basf)

- Dispersant: DISPERBYK-110 (manufactured by BYK)

- Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Experimental example

(1) Preparation of a barrier rib pattern cured film

A 5 cmХ5 cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the photosensitive resin compositions according to Examples 1 to 11 and Comparative Examples 1 to 7 was spin-coated on the glass substrate to a final film thickness of 10 μm, pre-baked at 100° C., and dried for 2 minutes to remove the solvent. Thereafter, a mask including a line/space pattern of 1 to 100 μm or a 40 mmХ40 mm pattern ^{was exposed at an exposure amount of 50 mJ/cm 2} , and the unexposed portion was removed using an aqueous alkali solution. The prepared cured film was then baked at 230° C. for 20 minutes to prepare a barrier rib pattern cured film having a thickness of 10 μm.

(2) Measurement of transmittance and reflectance

The transmittance and reflectance for each wavelength of the 40mmХ40mm pattern cured film prepared in the 10㎛ thickness were measured using a spectrophotometer (CM-3700d). At 450nm wavelength, when the transmittance was less than 5%, O, when it was 5% or more, it was denoted as X , when less than 30% was denoted by X, and the results are shown in Table 2, FIGS. 1 and 2 below.

(3) Measurement of line width change

A line of 100 μm using an optical microscope (ECLIPSE LV100POL, Nikon Corporation) for each of the substrate subjected to the development time of 80 seconds and the substrate having the development time of 160 seconds in the barrier rib pattern cured film manufacturing process of (1) above The line width of the mask pattern was measured. The change in the pattern line width of the substrate progressed for 80 seconds and the pattern line width change of the substrate proceeded for 160 seconds were measured, and the case where the line width change was 5.0 μm or more was denoted by X. The results are shown in Table 2 below.

450nm
transmittance 640nm
reflectivity 550nm
reflectivity line width change
(μm) Example 1 ○ ○ X 1.8 Example 2 ○ ○ X 0.3 Example 3 ○ ○ X 0.5 Example 4 ○ ○ X 3.7 Example 5 ○ ○ X 4.1 Example 6 ○ ○ ○ 0.7 Example 7 ○ ○ ○ 3.5 Example 8 ○ ○ ○ 0.4 Example 9 ○ ○ ○ 3.2 Example 10 ○ ○ X 0.4 Example 11 ○ ○ X 1.4 Comparative Example 1 ○ X X X Comparative Example 2 ○ X X X Comparative Example 3 X ○ X X Comparative Example 4 ○ X X X Comparative Example 5 ○ X X X Comparative Example 6 X X X X Comparative Example 7 X X X X

The cured film prepared using the photosensitive resin composition according to Examples 1 to 11 has a transmittance of less than 5% at a wavelength of 450 nm, a reflectance of 30% or more at a wavelength of 640 nm, and it can be confirmed that the change in the line width of the pattern is also excellent. have.

In particular, it can be seen that the cured film prepared by using the photosensitive resin composition according to Examples 6 to 9, which includes a yellow pigment as a colorant, also has a reflectance of 30% or more at a wavelength of 550 nm.

In contrast, the cured film prepared using the photosensitive resin composition according to Comparative Examples 1 and 2 not containing scattering particles exhibited a transmittance of less than 5% at a wavelength of 450 nm, but a reflectance of less than 30% at a wavelength of 640 nm. It can be seen that the change in the line width of the pattern is also very large.

In addition, the cured film prepared using the photosensitive resin composition according to Comparative Example 3 that does not contain a colorant exhibited a reflectance of 30% or more at a wavelength of 640 nm, but a transmittance of more than 5% at a wavelength of 450 nm, and the pattern It can be seen that the line width change is also very large.

In particular, the cured films prepared using the photosensitive resin compositions according to Comparative Examples 4 and 5 containing only a black colorant, not a red, yellow, or orange colorant as a colorant, exhibited a transmittance of less than 5% at a wavelength of 450nm, but scattering particles It can be seen that the reflectance of less than 30% at a wavelength of 640 nm was included even though it was included, so that the desired effect of the present invention could not be achieved.

Claims (13)

A photosensitive resin composition for forming a barrier rib comprising an alkali-soluble resin, a polymerizable compound, a photoinitiator and a solvent, the photosensitive resin composition comprising:
The cured film made of the photosensitive resin composition has a transmittance of less than 5% at a wavelength of 450 nm, and a reflectance of 30% or more at a wavelength of 640 nm, when the thickness of the cured film is 7 μm to 15 μm, the photosensitive resin composition for forming barrier ribs. The method according to claim 1,
The photosensitive resin composition further comprises at least one selected from a colorant and scattering particles, the photosensitive resin composition for forming barrier ribs. 3. The method according to claim 2,
The colorant comprises at least one selected from the group consisting of CI red pigment (CI Pigment Red), CI yellow pigment (CI Pigment Yellow) and CI orange pigment (CI Pigment Orange). 4. The method according to claim 3,
The CI red pigment (CI Pigment Red) is at least one selected from diketopyrrole-based, anthraquinone-based, perylene-based and azo-based photosensitive resin composition for forming barrier ribs. 4. The method according to claim 3,
The CI yellow pigment (CI Pigment Yellow) is at least one selected from anthraquinone-based, isoindolinone-based and azo-based photosensitive resin composition for forming barrier ribs. 4. The method according to claim 3,
The CI orange pigment (CI Pigment Orange) is at least one selected from quinophthalone-based, isoindolinone-based and diketopyrrole-based photosensitive resin composition for forming barrier ribs. 4. The method according to claim 3,
The CI red pigment is at least one selected from the group consisting of CI red pigments 177, 179, 254, 264 and 269,
The CI yellow pigment is at least one selected from the group consisting of CI yellow pigments 138, 139, 150 and 185,
The CI orange pigment is characterized in that at least one selected from the group consisting of CI orange pigments 64 and 71, the photosensitive resin composition for forming a barrier rib. 3. The method according to claim 2,
The scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO and A photosensitive resin composition for forming a barrier rib comprising at least one selected from the group consisting of MgO. The method according to claim 1,
The photosensitive resin composition is for forming a barrier rib of a color conversion panel using a blue light source, the photosensitive resin composition for forming a barrier rib. The method according to claim 1,
With respect to the total weight of solids in the photosensitive resin composition,
20 to 70% by weight of the alkali-soluble resin;
5 to 50% by weight of the polymerizable compound;
0.01 to 10% by weight of the photopolymerization initiator; and
With respect to the total weight of the photosensitive resin composition, characterized in that it contains 60 to 90% by weight of a solvent, the photosensitive resin composition for forming a barrier rib. The method according to claim 1,
When the cured film prepared from the photosensitive resin composition has a thickness of 7 µm to 15 µm, a reflectance of 30% or more at a wavelength of 550 nm, the photosensitive resin composition for forming a barrier rib. A barrier rib structure made of the photosensitive resin composition of any one of claims 1 to 11. A display device including the barrier rib structure of claim 12 .

Images