Photosensitive resin composition, pattern formed therefrom, and display device

Abstract

The present application provides a photosensitive resin composition, a pattern formed therefrom, and a display device, the photosensitive resin composition comprising scattering particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, the photosensitive resin composition being characterized in that the scattering particles are organic scattering particles, the difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound and the refractive index of the scattering particles is greater than 0.04, so that the dispersion stability of the dispersed scattering particles is excellent while a high haze value can be ensured, no residue is generated, and the adhesion to a substrate is excellent.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, patterns formed therefrom, and display devices. Background Technology

[0002] Photosensitive resin compositions are essential materials for color filters, liquid crystal display materials, organic light-emitting devices, displays, etc., and are used to form various cured patterns such as photoresists, insulating films, protective films, black matrices, and columnar spacers. Specifically, photosensitive resin compositions are selectively exposed and developed through photolithography processes to form desired patterns.

[0003] Specifically, the patterning of the photosensitive resin composition relies on photolithography, which involves polarity changes and cross-linking reactions of polymers caused by photoreaction. In particular, the formation of the aforementioned patterns utilizes the change in solubility in solvents such as alkaline aqueous solutions after exposure.

[0004] For photosensitive resin compositions, ensuring resistance to heat treatment, chemical etching, and gas etching processes used in the manufacturing process is crucial. In particular, recently, in order to improve light efficiency and effectively control the transmission and reflection of light in displays, patterns formed by photolithography require not only high reliability but also high refractive properties. Various components have been introduced into photosensitive resin compositions to impart high refractive properties to such patterns; however, there are issues where ensuring high refractive properties does not adequately guarantee reliability in areas such as heat resistance and solvent resistance.

[0005] Korean Patent Publication No. 10-2014-0086584 discloses a high-refractive-index photosensitive composition containing surface-modified titanium dioxide as scattering particles, but due to the high specific gravity of titanium dioxide, there is a limitation that it is difficult to ensure dispersion stability.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Korean Patent Publication No. 10-2014-0086584 Summary of the Invention

[0009] The technical issues to be solved

[0010] The present invention aims to improve the problems of the prior art and its purpose is to provide a photosensitive resin composition that has excellent dispersion stability of scattering particles to ensure high haze value, does not produce residue, and has excellent adhesion to the substrate.

[0011] Furthermore, the object of the present invention is to provide a pattern formed using the above-described photosensitive resin composition and a display device comprising the pattern.

[0012] However, the problems that this invention aims to solve are not limited to those mentioned above, and those skilled in the art will clearly understand from the following description other problems not mentioned.

[0013] Technical solution

[0014] To achieve the above objectives, the present invention provides a photosensitive resin composition comprising scattering particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, characterized in that the scattering particles are organic scattering particles, and the difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound and the refractive index of the scattering particles is greater than 0.04.

[0015] The scattering particles can be one or more particles selected from the group consisting of polyethylene, polypropylene, polyacrylonitrile, polyacrylate, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate, polystyrene, polyurethane and melamine.

[0016] The particle size D50 of the scattering particles can be from 400 to 1500 nm.

[0017] The refractive index of the scattering particles at a wavelength of 550 nm can be between 1.4 and 1.8.

[0018] The content of the scattering particles can be from 0.1 to 50% by weight relative to the total weight of the solid components in the photosensitive resin composition.

[0019] The photopolymerizable compound may contain one or more compounds selected from those represented by chemical formulas 1 to 10 below:

[0020] [Chemical Formula 1]

[0021]

[0022] [Chemical Formula 2]

[0023]

[0024] [Chemical Formula 3]

[0025]

[0026] [Chemical Formula 4]

[0027]

[0028] [Chemical Formula 5]

[0029]

[0030] [Chemical Formula 6]

[0031]

[0032] [Chemical Formula 7]

[0033]

[0034] [Chemical Formula 8]

[0035]

[0036] [Chemical Formula 9]

[0037]

[0038] [Chemical Formula 10]

[0039] .

[0040] Furthermore, the present invention provides a pattern comprising a cured product of the photosensitive resin composition.

[0041] Furthermore, the present invention provides a display device comprising the pattern.

[0042] The effects of the invention

[0043] The present invention provides a photosensitive resin composition that has excellent dispersion stability of scattering particles to ensure high haze value, does not produce residue, and has excellent adhesion to the substrate.

[0044] Furthermore, the present invention can provide a pattern formed using the photosensitive resin composition and a display device comprising the pattern. Detailed Implementation

[0045] This invention relates to a photosensitive resin composition, a pattern formed therefrom, and a display device. The photosensitive resin composition comprises scattering particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The photosensitive resin composition is characterized in that the scattering particles are organic scattering particles, and the difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound and the refractive index of the scattering particles is greater than 0.04.

[0046] This invention utilizes organic scattering particles containing refractive indexes greater than 0.04, which exhibit excellent dispersion stability and ensure high haze values. Furthermore, experiments have confirmed the availability of a photosensitive resin composition that does not produce residue and exhibits excellent adhesion to the substrate, thus completing this invention. Specifically, the difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound and the refractive index of the scattering particles can be 0.05 or higher.

[0047] The components constituting the photosensitive resin composition of the present invention will now be described in detail. However, the present invention is not limited to these components.

[0048] In this invention, the total weight of solid components in the photosensitive resin composition refers to the total weight of all components in the photosensitive resin composition except for the solvent.

[0049] As used in this specification, “(meth)acrylate” includes and refers to acrylates and / or methacrylates.

[0050] The terms “comprises” and / or “comprising” as used in this specification are used to mean that the presence or addition of more than one other constituent element besides the mentioned constituent element is not excluded.

[0051] <Photosensitive Resin Composition>

[0052] The photosensitive resin composition of the present invention comprises scattering particles, alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, and solvent.

[0053] Scattering particles

[0054] The scattering particles of the present invention are particles that scatter and reflect incident light, and may include organic particles as scattering particles.

[0055] When inorganic materials such as metal oxides are included as scattering particles in the photosensitive resin composition of the present invention, the high specific gravity of the scattering particles will cause them to settle naturally, resulting in a problem that makes it difficult to ensure dispersion stability. Therefore, it is preferable to include organic particles as scattering particles.

[0056] The type of organic particles is not particularly limited as long as they can perform the function of scattering and reflecting light while having a refractive index of 1.4 to 1.8, preferably 1.45 to 1.7, at a wavelength of 550 nm. Specifically, examples of such organic particles include polyethylene, polypropylene, polyacrylonitrile, polyacrylate, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate, polystyrene, polyurethane, melamine, etc., and one or more of these substances can be used.

[0057] In one embodiment of the present invention, the particle size D50 of the scattering particles can be from 400 to 1500 nm, preferably from 400 to 1200 nm. If the particle size D50 is within the above range, scattering characteristics such as transmittance can be ensured, and no residue is generated during pattern formation, which is therefore preferred. When the particle size D50 of the scattering particles is lower than the above range, the possibility of residue generation due to particle aggregation increases with the increase of the surface area of ​​the scattering particles; if it exceeds the above range, the pattern developability deteriorates, and the possibility of residue generation increases, which is therefore not preferred.

[0058] In this invention, particle size D50 can refer to the diameter of particles that, after particle size analysis, reach a cumulative 50% volume percentage. The method for determining the particle size is not particularly limited; laser diffraction (LD) or similar methods can be used. More specifically, it can be determined by wet particle size analysis (PSA) using short-wavelength lasers.

[0059] The content of the scattering particles can be from 0.1% to 50% by weight relative to the total weight of the solid components in the photosensitive resin composition, preferably from 5% to 40% by weight. When the content of the scattering particles is within the above range, the refractive index of the pattern can be ensured, and the stability of the composition can be ensured, which is therefore preferred.

[0060] Regarding the scattering particles, from the perspective of ensuring the haze value of the pattern, the difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound (described later) and the refractive index of the scattering particles can be greater than 0.04, preferably greater than 0.05. When the refractive index difference is lower than the above range, a sufficient haze value cannot be ensured, resulting in a decrease in the light efficiency of the pattern formed by the composition. Therefore, it is preferable that the refractive index difference is included within the above range.

[0061] Alkali-soluble resins

[0062] The alkali-soluble resin of the present invention can be selected from resins known in the art without particular limitation, as long as it has reactivity and alkali solubility under the action of light or heat, functions as a dispersion medium for solid components including colorants, and functions as a binder resin.

[0063] Specifically, the alkali-soluble resin is preferably a copolymer of a monomer containing an unsaturated carboxyl group and other monomers that can be copolymerized with it.

[0064] Examples of monomers containing unsaturated carboxyl groups include unsaturated carboxylic acids, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids, which have one or more carboxyl groups in their molecules.

[0065] Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

[0066] Examples of unsaturated dicarboxylic acids mentioned above include maleic acid, fumaric acid, itaconic acid, citraconic acid, and medoconic acid.

[0067] The aforementioned unsaturated polycarboxylic acids can be acid anhydrides, specifically maleic anhydride, itaconic anhydride, and citraconic anhydride. Furthermore, these unsaturated polycarboxylic acids can be their mono(2-methacryloyloxyalkyl) esters, such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, and mono(2-methacryloyloxyethyl) phthalate. These unsaturated polycarboxylic acids can also be mono(meth)acrylates of their dicarboxylic acid polymers, such as ω-carboxylated polycaprolactone monoacrylate and ω-carboxylated polycaprolactone monomethacrylate. The aforementioned carboxyl-containing monomers can be used individually or in combination of two or more.

[0068] Other monomers that can copolymerize with the aforementioned carboxyl-containing monomers include, for example, 3,4-epoxytricyclo[5.2.1.0]. 2,6 ] Decane-9-yl acrylate, 3,4-epoxy tricyclic [5.2.1.0] 2,6Epoxy (meth)acrylate compounds such as decane-8-yl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether; aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, and methyl... Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate Hexyl acrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glyceryl monoacrylate Unsaturated carboxylic acid esters such as oleic acid esters and glyceryl monomethacrylate; unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; and carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylonitrile, N-2-hydroxyethylacrylonitrile, and N-2-hydroxyethylmethacrylonitrile; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and macromonomers whose polymer chains of polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysiloxane have monoacryloyl or monomethacryloyl groups at the end. These monomers can be used individually or in combination of two or more.

[0069] In one embodiment of the present invention, the alkali-soluble resin may be a copolymer represented by the following chemical formula 11.

[0070] [Chemical Formula 11]

[0071]

[0072] In the above chemical formula 11,

[0073] X is a base represented by the following chemical formula 12.

[0074] Y represents the residue remaining after removing the carboxylic anhydride group (-CO-O-CO-) from the dicarboxylic anhydrides contained in maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, chlorogenic anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride.

[0075] Z represents the residue remaining after removing two carboxylic anhydride groups from tetracarboxylic anhydrides such as pyromellitic tetracarboxylic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

[0076] [Chemical Formula 12]

[0077]

[0078] In the above chemical formula 12,

[0079] * indicates a bonding bond.

[0080] The acid value of the aforementioned alkali-soluble resin can be from 10 mg·KOH / g to 150 mg·KOH / g. This acid value is determined as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and is typically obtained by titration using an aqueous potassium hydroxide solution. If the acid value is within the above range, the solubility in the developer is improved, making the non-exposed areas easier to dissolve and increasing sensitivity. As a result, the pattern in the exposed areas remains during development, improving the film remaining ratio, which is therefore preferable.

[0081] For the aforementioned alkali-soluble resin, the converted weight-average molecular weight (hereinafter referred to as "weight-average molecular weight") of polystyrene, determined by gel permeation chromatography (GPC; with tetrahydrofuran as the elution solvent), can be from 3,000 to 200,000, preferably from 5,000 to 100,000. If the weight-average molecular weight is within the above range, the hardness of the coating film is increased, resulting in a high film retention rate, and the solubility in the non-exposed areas of the developer is excellent, thus improving the resolution, which is therefore preferred.

[0082] The molecular weight distribution [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] of the above-mentioned alkali-soluble resin can be from 1.5 to 6.0, preferably from 1.8 to 4.0. If the molecular weight distribution is within the above range, the developability is excellent, and therefore it is preferred.

[0083] The content of the alkali-soluble resin can be 1 to 70% by weight relative to the total weight of the solid components in the photosensitive resin composition, preferably 20 to 60% by weight. When the content of the alkali-soluble resin is within the above range, it is easy to obtain a photosensitive resin composition with excellent developability and a cured film with excellent chemical resistance, which is therefore preferred.

[0084] Photopolymer compounds

[0085] The photopolymerizable compound of the present invention is a compound that can be polymerized under the action of light and a photopolymerization initiator to be described later. It improves the mechanical properties of the colored pattern or supplements the developability of the alkali-soluble resin by polymerizing through the exposure process.

[0086] Examples of photopolymerizable compounds include: monofunctional monomers such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpyrrolidone; difunctional monomers such as 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, or 3-methylpentyl glycol di(meth)acrylate; and trimethylolpropane tri(meth)acrylate. Multifunctional monomers such as ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate; difunctional or multifunctional acrylate monomers based on aromatic tetracarboxylic acids derived from diphenylsulfone tetracarboxylic dianhydride or 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

[0087] Examples of difunctional or polyfunctional acrylate monomers based on aromatic tetracarboxylic acids include compounds represented by chemical formulas 1 to 10 below, and from the perspective of ensuring high refractive properties of the pattern, it is preferable to include one or more compounds selected from those represented by chemical formulas 1 to 10 below:

[0088] [Chemical Formula 1]

[0089]

[0090] [Chemical Formula 2]

[0091]

[0092] [Chemical Formula 3]

[0093]

[0094] [Chemical Formula 4]

[0095]

[0096] [Chemical Formula 5]

[0097]

[0098] [Chemical Formula 6]

[0099]

[0100] [Chemical Formula 7]

[0101]

[0102] [Chemical Formula 8]

[0103]

[0104] [Chemical Formula 9]

[0105]

[0106] [Chemical Formula 10]

[0107] .

[0108] The content of the photopolymerizable compound can be 5 to 70% by weight relative to the total weight of the solid components in the photosensitive resin composition, preferably 10 to 50% by weight. When the content of the photopolymerizable compound is lower than the above range, it may cause a decrease in pixel strength; when the content is higher than the above range, it may cause a decrease in smoothness. Therefore, considering the strength or flatness of the pixel, it is preferable that the content of the photopolymerizable compound is within the above range.

[0109] Photopolymerization initiator

[0110] The photopolymerization initiator of the present invention is a compound used to initiate the polymerization of the above-mentioned photopolymerizable compounds. Photopolymerization initiators used in the art can be used without limitation as long as the purpose of the present invention is not impaired.

[0111] Specifically, the aforementioned photopolymerization initiators can be acetophenone-based, benzophenone-based, triazine-based, thioxanone-based, oxime-based, benzoin-based, and biimidazole-based compounds, which can be used individually or in combination of two or more. Examples of the aforementioned oxime compounds include o-ethoxycarbonyl-α-oxoimino-1-phenylpropane-1-one and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(o-acetyl oxime).

[0112] Commercially available photopolymerization initiators include, but are not limited to, PBG-327, PBG-329, PBG-305 (manufactured by TRONLY), NCI-831E (manufactured by ADEKA), OXE-01, OXE-02 (manufactured by Ciba) and N-1919 (manufactured by ADEKA).

[0113] The content of the photopolymerization initiator relative to the total weight of the solid components in the photosensitive resin composition can be from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight. This range is set considering the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film. When the content of the photopolymerization initiator is below this range, the polymerization rate may be low, resulting in a longer overall process time. When the content is above this range, over-reaction may occur, leading to a decrease in the physical properties of the coating film after the cross-linking reaction. Therefore, the content is preferably within the above range.

[0114] solvent

[0115] The solvent of the present invention can be any organic solvent commonly used in the art without particular limitation. Examples of such solvents include ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters, and more than one of them can be used, but the invention is not limited thereto.

[0116] For example, examples include: ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, and dipropylene glycol diethyl ether; and methyl cellosolve acetate and ethyl cellosolve acetate. Ethylene glycol alkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, etc., alkylene glycol alkyl ether acetates; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc.

[0117] The solvents mentioned above are preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate, etc.; more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. These solvents can be used individually or in combination of two or more.

[0118] The content of the solvent relative to the total weight of the photosensitive resin composition can be 10 to 90% by weight, preferably 15 to 85% by weight, but is not limited thereto. When the content of the solvent is within the above range, the flatness during coating tends to improve, and is therefore preferred.

[0119] additive

[0120] The present invention may further include additives as needed. For example, it may further include one or more of the following: selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and anti-gelling agents.

[0121] Specific examples of the other polymer compounds mentioned above include thermosetting resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes.

[0122] The aforementioned curing agents are used to achieve deep curing and improve mechanical strength. Specific examples include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0123] Among the aforementioned curing agents, specific examples of epoxy compounds include: bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenolic varnish type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, (meth)acrylate glycidyl ester (co)polymers, triglycidyl isocyanurate, etc.

[0124] Specific examples of oxetane compounds in the curing agent include carbonate oxetane, xylene oxetane, adipate oxetane, terephthalate oxetane, and cyclohexane dicarboxylic acid oxetane.

[0125] The aforementioned curing agent can be used in conjunction with a curing aid compound, which, together with the curing agent, enables the ring-opening polymerization of the epoxy groups of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of such curing aid compounds include polycarboxylic acids, polycarboxylic anhydrides, and acid-generating agents. Commercially available epoxy resin curing agents can be used as polycarboxylic anhydrides. Specific examples of such epoxy resin curing agents include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Industries, Ltd.), RIKACID HH (trade name, manufactured by Shin Nippon Rikka Co., Ltd.), and MH-700 (trade name, manufactured by Shin Nippon Rikka Co., Ltd.). These curing agents can be used individually or in combination of two or more.

[0126] The surfactants described above can be used to further improve the film-forming properties of the photosensitive resin composition, and preferably silicone surfactants or fluorinated surfactants can be used.

[0127] For the aforementioned silicone-based surfactants, examples of commercially available products include: Dow Corning Toray Silicones' DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400; and GE Toshiba Silicones' TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452. For the aforementioned fluorinated surfactants, examples of commercially available products include MEGAFACE F-470, F-471, F-475, F-482, F-489, and F-554 (Dai Nippon Ink & Chemical Co., Ltd.), BM-1000 and BM-1100 (BM Chemie), and Fluorad FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.). These surfactants can be used individually or in combination of two or more.

[0128] The aforementioned adhesion promoter is an additive used to improve the coating and adhesion to the substrate, and may contain a silane coupling agent having reactive substituents selected from the group consisting of carboxyl, methacryloyl, isocyanate, epoxy, and combinations thereof.

[0129] Among the aforementioned adhesion promoters, specific examples of silane coupling agents include: trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0130] Specific examples of the aforementioned antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

[0131] Specific examples of the aforementioned ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0132] Specific examples of the aforementioned anti-condensing agents include sodium polyacrylate.

[0133] For additives not listed in the above description, they may be appropriately added by those skilled in the art without impairing the effects of the present invention. For example, the amount of the above additives used relative to the total weight of the photosensitive resin composition may be 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, but is not limited thereto.

[0134] <Pattern>

[0135] The present invention provides a pattern formed using the above-described photosensitive resin composition.

[0136] Apart from being formed by the above-described photosensitive resin composition, the pattern can be manufactured by methods known in the art. In the formation of a photocurable pattern, the pattern can be formed by a photolithography method that involves coating the above-described photosensitive resin composition onto a substrate and then exposing and developing the substrate.

[0137] According to an embodiment of the present invention, a conventional patterning process for forming a pattern by photolithography includes:

[0138] a) The step of coating a photosensitive resin composition onto a substrate;

[0139] b) The VCD (Vacuum Dry) step, in which the solvent is evaporated by depressurization;

[0140] c) Pre-drying step to dry the solvent;

[0141] d) The step of aligning a photomask onto the obtained film and irradiating it with active light to cure the exposed portion;

[0142] e) The step of using an alkaline aqueous solution to dissolve the unexposed portion during the developing process; and

[0143] f) Perform the drying and post-drying steps.

[0144] The aforementioned substrate uses a glass substrate or a polymer board. As a glass substrate, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz are particularly preferred. Furthermore, as a polymer board, examples include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, or polysulfone.

[0145] At this point, coating can be performed using wet coating methods with coating devices such as roller coaters, spin coaters, slot coaters, slot coaters (sometimes also called die coaters), and inkjet printers to achieve the desired thickness.

[0146] Pre-drying is carried out using heating methods such as ovens and hot plates. The heating temperature and time during pre-drying are appropriately selected according to the solvent used, and can be performed at low temperatures, such as 80 to 150°C or 80 to 100°C for 1 to 30 minutes.

[0147] Furthermore, the pre-baking followed by exposure is performed using an exposure machine, with exposure through a photomask, exposing only the portion corresponding to the pattern. The light used in this process can be, for example, visible light, ultraviolet light, X-rays, or electron beams.

[0148] Alkaline development after exposure is performed to remove the colored photosensitive resin composition from the unexposed areas, thereby forming a desired pattern. Suitable developing solutions for this alkaline development include, for example, aqueous solutions of alkali metal or alkaline earth metal carbonates. In particular, an alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, or lithium carbonate is used at a temperature range of 10 to 50°C, preferably 20 to 40°C, performed using a developing machine or an ultrasonic cleaner.

[0149] Post-baking is performed to improve the adhesion between the patterned film and the substrate. Post-baking can be performed at low temperatures, such as 80 to 150°C or 80 to 100°C, for 10 to 120 minutes via heat treatment. Like pre-baking, post-baking is performed using an oven, hot plate, etc.

[0150] The aforementioned pattern may be a photocurable pattern selected from the group consisting of array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored photoresist pattern, pattern containing scatterers, and pattern containing quantum dots, but is not limited thereto.

[0151] <Display Device>

[0152] The present invention provides a display device including the above-described pattern.

[0153] In addition to having the above-mentioned pattern, the display device may further include configurations known in the art.

[0154] Specifically, examples include liquid crystal displays (LCDs), organic EL displays (including organic EL displays, OLEDs and QLEDs), flexible displays, liquid crystal projectors, display devices for game consoles, display devices for portable terminals such as mobile phones, display devices for digital cameras, and navigation display devices, but are not limited to these.

[0155] The present invention will be described in more detail below through embodiments.

[0156] However, the following embodiments are used to illustrate the present invention in a more specific way, and the scope of the present invention is not limited by the following embodiments. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

[0157] In addition, unless otherwise specified, the "%" and "parts" used to indicate content in the following text are based on weight.

[0158] Synthesis Example 1: Preparation of Photopolymerizable Compounds (C-1)

[0159] Under a dry nitrogen stream, 4.58 g (0.01 mol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dihydride, 2.32 g (0.02 mol) of 2-hydroxyethyl acrylate, and 0.17 g (0.001 mol) of p-toluenesulfonic acid (p-TSA) were added. 100 mL of anhydrous tetrahydrofuran was then added, and the mixture was stirred at 70 °C for 5 hours. After the reaction was complete, the product was filtered under reduced pressure to remove all solvents and washed with a 20% methanol / water mixture, thereby synthesizing compound C-1 of formula 1.

[0160] [Chemical Formula 1]

[0161]

[0162] The obtained product was confirmed by FT-IR and elemental analysis. FT-IR analysis of the product detected OH stretching vibrations (2500–3300 cm⁻¹) corresponding to the COOH groups formed during ring opening. -1 ) and the C=C stretching vibration of acrylate groups (1635 cm⁻¹) -1 The spectrum showed bands, but no corresponding symmetric or asymmetric C=O stretching vibrations (1851 cm⁻¹) were found corresponding to the anhydride group. -1 and 1778cm -1 The peak of the product indicated the formation of compound C-1. Furthermore, elemental analysis confirmed the following: theoretical values: C 67.82%, H 4.38%, O 27.80%; actual values: C 67.71%, H 4.33%, O 27.96%.

[0163] Synthesis Example 2: Preparation of Photopolymerizable Compounds (C-2)

[0164] Under a dry nitrogen stream, 6.91 g (0.01 mol) of compound C-1 and 1.41 g (0.01 mol) of 2-isocyanatoethyl acrylate were added. 100 mL of anhydrous tetrahydrofuran was then added, and the mixture was stirred at 70 °C for 12 hours. After the reaction was complete, the product was filtered under reduced pressure to remove all solvents and washed with a 20% methanol / water mixture, thereby synthesizing compound C-2 of formula 2.

[0165] [Chemical Formula 2]

[0166]

[0167] The product was confirmed by FT-IR and elemental analysis. FT-IR analysis of the product detected the C=O stretching vibration (1670 cm⁻¹) corresponding to the amide group. -1 The presence of the spectral band indicated the formation of compound C-2. Furthermore, elemental analysis of the product confirmed the following: theoretical values: C 67.09%, H 4.73%, N 1.78%, O 26.40%; actual values: C 67.01%, H 4.76%, N 1.82%, O 26.41%.

[0168] Polymerization Example 1: Synthesis of Alkali-Soluble Resins (B-1)

[0169] In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of azobisisobutyronitrile (AIBN), 30.0 parts by weight of acrylic acid, 40.0 parts by weight of methyl methacrylate, and 30 parts by weight of vinyltoluene monomer were added, followed by nitrogen purging. The reaction mixture was then heated to 110°C with stirring and reacted for 6 hours. Next, 10.0 parts by weight of glycidyl methacrylate (with a carboxyl group content of 33% relative to the acrylic acid used in this reaction), 1.5 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 3 parts by weight of triethylamine were added to the flask, and the reaction was carried out at 110°C for 8 hours, thereby obtaining an alkali-soluble resin (B-1) with a solid acid value of 90 mg KOH / g and a weight-average molecular weight (Mw) of 5,500 as determined by GPC.

[0170] Polymerization Example 2: Synthesis of Alkali-Soluble Resins (B-2)

[0171] After setting up a reflux condenser and thermometer in a three-necked flask, 42.5 g of 9,9-bisphenol fluorene was added, followed by 220 mL of 2-(chloromethyl)ethylene oxide. 100 mg of tetrabutylammonium bromide was added, and the mixture was stirred while the temperature was raised to 90 °C. After confirming that the unreacted content was below 0.3%, vacuum distillation was performed. The temperature was lowered to 30 °C, and dichloromethane was added, followed by slow addition of NaOH. After confirming that the product purity was above 96% by high-performance liquid chromatography (HPLC), 5% HCl was added dropwise to terminate the reaction. The reactants were extracted and separated into layers; the organic layer was washed with water until neutral. The organic layer was dried with MgSO4 and then concentrated by vacuum distillation using a rotary evaporator. Dichloromethane was added to the concentrated product, and the mixture was heated to 40 °C while stirring. Methanol was added, the solution temperature was lowered, and the mixture was stirred. The resulting solid was filtered and dried under vacuum at room temperature to obtain 52.7 g of a white solid powder. The obtained white solid powder was placed in a three-necked flask, and 27 g of thiophenol and 32 g of ethanol were added and stirred. 16.3 g of triethylamine was slowly added dropwise to the reaction solution. After the reaction was complete, the ethanol was removed by vacuum distillation. The organic matter was dissolved in dichloromethane and washed with water, and the dichloromethane was removed by vacuum distillation. An equal volume of PGMEA solvent was added to the three-necked flask to prepare a 50% solution, and the temperature was raised to 115 °C. 31.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was added dropwise at 115 °C, and the mixture was stirred for 6 hours while maintaining the temperature at 115 °C. 7.35 g of phthalic anhydride was added, and the reaction was terminated after further stirring for 2 hours. After cooling, an alkali-soluble resin (B-2) with a weight-average molecular weight of 5,000 g / mol as determined by GPC was obtained.

[0172] Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions

[0173] The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared according to the components and contents in Table 1 below.

[0174] [Table 1]

[0175]

[0176] - A-1: ​​PMMA (polymethyl methacrylate), D50=1000nm

[0177] - A-2: PS (polystyrene), D50=1000nm

[0178] - A-3: PU (Polyurethane), D50=1000nm

[0179] - A-4: Melamine, D50 = 1000nm

[0180] - A'-1: ZnO, D50=400nm

[0181] - A'-2: TiO2, D50=200nm

[0182] - A'-3: PMMA (polymethyl methacrylate), D50=200nm

[0183] - A'-4: PMMA (polymethyl methacrylate), D50=1800nm

[0184] - B-1: Alkali-soluble resin of Polymerization Example 1

[0185] - B-2: Alkali-soluble resin of Polymerization Example 2

[0186] - C-1: Photopolymerizable compound from Synthetic Example 1

[0187] - C-2: Photopolymerizable compound from Synthetic Example 2

[0188] - C-3: Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

[0189] - D: OXE-01 (Ciba)

[0190] - E: Propylene glycol monomethyl ether acetate (PGMEA)

[0191] Experimental Example

[0192] Using the photosensitive resin compositions manufactured in the above examples and comparative examples, after patterns were manufactured as described below, the refractive index, developability, residue and adhesion of the manufactured patterns were evaluated, and the results are recorded in Table 2 below.

[0193] Pattern making

[0194] A 5 × 5 cm glass substrate (Eagle 2000; manufactured by Corning Incorporated) was sequentially cleaned with neutral detergent, water, and alcohol, and then dried. The photosensitive resin compositions prepared in the above examples and comparative examples were spin-coated onto the glass substrate, and then pre-baked at 85°C for 120 seconds using a hot plate. After cooling the pre-baked substrate to room temperature, a test photomask with a line / pitch pattern of 1 μm to 50 μm was placed on it and heated at 50 mJ / cm². 2 The film was irradiated with light at an exposure level (based on 365 nm). After irradiation, it was developed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 100 seconds, washed with ultrapure water, and dried under nitrogen, thereby forming a pattern on the photosensitive resin composition film. The film was then post-baked at 90°C for 1 hour in an oven, resulting in a film thickness of 2 μm.

[0195] (1) Refractive index measurement

[0196] For the mixtures of scattering particles, alkali-soluble resins, and photopolymerizable compounds corresponding to those in Table 1 in the compositions of the above examples and comparative examples, linear polarization was measured using an ellipsometer (JA Woollam, M-2000) at 25°C and 50%RH with incident angles of 65°, 70°, and 75° in the wavelength range of 200 nm to 1000 nm. Using CompleteEASE software, the measured linear polarization data (Ψ, Δ) were optimized and fitted using the Cauchy model of Equation 1 below to achieve an MSE of 70 or less to calculate the refractive index at a wavelength of 550 nm. The results are shown in Table 2 below.

[0197] <Mathematical Formula 1>

[0198]

[0199] In Equation 1 above, n(λ) is the refractive index at wavelength λ, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

[0200] (2) Haze Evaluation

[0201] Except for the absence of a mask, a cured film formed by exposure was manufactured according to the above pattern manufacturing method. The haze of the prepared cured film was evaluated using an HM-150 (Murakami Color Research Laboratory), and the results are shown in Table 2 below.

[0202] (3) Residue Evaluation

[0203] For the embodiments and comparative examples, the presence of residue around the pattern obtained by the above pattern manufacturing method was observed by optical microscope, and the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 2 below.

[0204] ○: No residue

[0205] ×: There are residues.

[0206] (4) Evaluation of Dispersion Stability

[0207] For the compositions manufactured in the above embodiments and comparative examples, using a TURBISCAN LAB (stability analyzer), 20 ml of the composition was placed in a 40 ml vial for dispersion stability analysis. After standing at room temperature for 24 hours, the TSI (dispersion stability index) after standing for 24 hours was calculated according to the following mathematical formula 2. The results are shown in Table 2 below. The smaller the TSI value, the better the dispersion stability.

[0208] <Mathematical Formula 2>

[0209] Definition of TSI (Turbiscan Stability Index)

[0210]

[0211] In Equation 2 above, H (mm) is the total height of the sample, and scan... i (h)-scan i-1 (h) The difference in distance (di, distance) between the curve of the i-th scan and the curve of the (i-1)-th scan.

[0212] [Table 2]

[0213]

[0214] Based on the above experimental results, it can be confirmed that the refractive index difference between the scattering particles and the mixture of alkali-soluble resin and photopolymerizable compound contained in the photosensitive resin compositions of Examples 1 to 6 at a wavelength of 550 nm is greater than 0.05, which results in an excellent haze value. Furthermore, the dispersion stability is less than 1.5 without producing residue, thus exhibiting excellent stability.

[0215] In contrast, Comparative Example 1, with a refractive index difference of 0.01 between the scattering particles and the mixture, exhibited a low haze value and poor scattering characteristics, rendering it unsuitable as an effective scattering material. Comparative Examples 2 to 3, which did not contain organic scattering particles, produced residue around the pattern and exhibited high dispersion stability values, confirming that the scattering particles had settled. Comparative Example 4, containing small-sized scattering particles, showed particle agglomeration and residue formation. Comparative Example 5, containing large-sized scattering particles, showed poor developability and residue formation.

Claims

1. A photosensitive resin composition comprising scattering particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, characterized in that, The scattering particles are organic scattering particles. The difference between the refractive index of the mixture of the alkali-soluble resin and the photopolymerizable compound and the refractive index of the scattering particles is greater than 0.

04.

2. The photosensitive resin composition according to claim 1, wherein, The scattering particles are selected from one or more particles chosen from the group consisting of polyethylene, polypropylene, polyacrylonitrile, polyacrylate, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate, polystyrene, polyurethane, and melamine.

3. The photosensitive resin composition according to claim 1, wherein, The particle size D50 of the scattering particles is 400 to 1500 nm.

4. The photosensitive resin composition according to claim 1, wherein, The scattering particles have a refractive index of 1.4 to 1.8 at a wavelength of 550 nm.

5. The photosensitive resin composition according to claim 1, wherein, The content of the scattering particles is 0.1 to 50% by weight relative to the total weight of the solid components in the photosensitive resin composition.

6. The photosensitive resin composition according to claim 1, wherein, The photopolymerizable compound comprises one or more compounds selected from those represented by chemical formulas 1 to 10 below: Chemical Formula 1 Chemical formula 2 Chemical formula 3 Chemical Formula 4 Chemical formula 5 Chemical Formula 6 Chemical Formula 7 Chemical Formula 8 Chemical formula 9 Chemical Formula 10 。 7. A pattern comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6.

8. A display device comprising the pattern of claim 7.

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