Light-shielding Photosensitive resin composition, cured product thereof, method for forming pattern, and method for producing photosensitive resin composition

Abstract

The present invention relates to a light-shielding photosensitive resin composition, a cured product thereof, a method for forming a pattern, and a method for manufacturing a photosensitive resin composition. Specifically, it relates to a light-shielding photosensitive resin composition containing a polysilsesquioxane binder that has excellent chemical resistance, does not degrade in light-shielding performance during an OLED process, and does not cause deformation of the film, a cured product thereof, a method for forming a pattern, and a method for manufacturing a photosensitive resin composition.

Description

Technology Field

[0001] The present invention relates to a light-shielding photosensitive resin composition, a cured product thereof, a method for forming a pattern, and a method for manufacturing a photosensitive resin composition. Specifically, it relates to a light-shielding photosensitive resin composition containing a polysilsesquioxane binder that has excellent chemical resistance, does not degrade in light-shielding performance during an OLED process, and does not cause deformation of the film, a cured product thereof, a method for forming a pattern, and a method for manufacturing a photosensitive resin composition. Background Technology

[0002] Conventionally, OLED pixels have been patterned using methods such as screen printing, roll-to-roll, and laser direct patterning. In addition, photolithography using a photoresist composition is performed in the patterning process of OLED display manufacturing. Through photolithography, large-area OLED pixels can be patterned, and OLED pixels at ultra-fine units can be patterned, thereby enabling the realization of a high-resolution display screen.

[0003] To realize high-density, integrated, and ultra-high-resolution OLED display screens, forming ultra-fine patterns remains crucial. Methods for forming ultra-fine patterns include the positive method and the negative method. The positive method forms a pattern by removing the exposed portion of the photoresist composition, while the negative method forms a pattern by removing the unexposed portion of the photoresist composition.

[0004] The photoresist compositions used for the positive and negative methods are distinguished. Among these, the photoresist composition for the negative method must have developability so that unexposed areas can be removed. Conventional negative-type photoresist photosensitive resin compositions contain acid functional groups in the binder, so development was performed using alkaline developers such as KOH and TMAH (Tetramethyl Ammonium Hydroxide). Negative-type photosensitive resin compositions with improved developability have been disclosed, for example, Registered Patent No. 10-2585445 (Oct. 05, 2023), Registered Patent No. 10-1787651 (Oct. 18, 2017), and Registered Patent No. 10-1306778 (September 17, 2013). The problem to be solved

[0005] A negative-type photosensitive resin composition may contain an alkali-soluble resin or binder so that the unexposed portion can be removed. Examples of binders proposed include acrylic resin, polyimide resin, phenolic resin, polyurethane resin, polyester resin, polyvinyl alcohol resin, epoxy resin, etc.

[0006] In addition, polysilsesquioxane binders are copolymers of polysiloxanes that exhibit excellent chemical resistance, making them suitable for use in photosensitive resin compositions. However, since polysilsesquioxanes are synthesized via a sol-gel reaction using acid / base catalysts, it has been difficult to introduce acid functional groups into the binder itself, as is the case with conventional binders. Consequently, most polysilsesquioxane binders do not dissolve well in alkaline developers, resulting in poor developability; thus, despite the advantages of the aforementioned properties of polysilsesquioxane binders, it remains difficult to apply them to negative-type photosensitive resin compositions.

[0007] Accordingly, the aim was to provide a polysilsesquioxane-based binder having developability in alkaline aqueous solutions and a light-blocking photosensitive resin composition containing the same by controlling the acid functional groups and double bonds within the polysilsesquioxane structure. means of solving the problem

[0008] According to one aspect of the present invention, the composition comprises a binder, a pigment dispersion, a polyfunctional monomer, a photoinitiator, and a solvent, and

[0009] The above binder includes a polysilsesquioxane-based binder, and

[0010] The above polysilsesquioxane-based binder may provide a light-shielding photosensitive resin composition comprising double bonds.

[0011] Preferably, a light-shielding photosensitive resin composition may be provided in which the double bond is derived from an ester compound, a methacrylic oxygen group-containing compound, an acrylic oxygen group-containing compound, a methacrylic group-containing compound, an acrylic group-containing compound, a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound.

[0012] Preferably, the polysilsesquioxane-based binder can provide a light-shielding photosensitive resin composition that further comprises an acid functional group.

[0013] Preferably, a light-shielding photosensitive resin composition can be provided in which the acid functional group is derived from a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound.

[0014] Preferably, a light-blocking photosensitive resin composition can be provided in which the acid functional group is derived from a succinic acid compound.

[0015] Preferably, the succinic acid compound is a succinic anhydride compound, and a light-blocking photosensitive resin composition can be provided.

[0016] Preferably, the binder comprises 10 to 30 parts by weight;

[0017] The above pigment dispersion is 40 to 60 parts by weight;

[0018] The above polyfunctional monomer is 1 to 20 parts by weight;

[0019] The above photoinitiator comprises 0.1 to 5 parts by weight; and

[0020] A light-shielding photosensitive resin composition may be provided, comprising 10 to 30 parts by weight of the above solvent.

[0021] Preferably, the succinic acid compound may provide a light-blocking photosensitive resin composition in which triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride, or trimethoxysilylbutyl succinic anhydride.

[0022] Preferably, a light-shielding photosensitive resin composition can be provided in which the change in optical density (OD) before and after immersing the film formed from the light-shielding photosensitive resin composition in an acidic solvent is less than 20%.

[0023] Preferably, after immersing a film formed from the light-shielding photosensitive resin composition in an acidic solvent, a light-shielding photosensitive resin composition having an adhesion strength of 5B to 3B according to ASTM D3359 can be provided.

[0024] Preferably, a light-shielding photosensitive resin composition can be provided in which the change in film thickness before and after immersion of the film formed from the light-shielding photosensitive resin composition in an acidic solvent is less than 7%.

[0025] Preferably, a light-shielding photosensitive resin composition can be provided in which the minimum size of a pattern produced by the light-shielding photosensitive resin composition is less than 10 μm.

[0026] According to another aspect of the present invention, a cured product prepared by curing the light-blocking photosensitive resin composition can be provided.

[0027] According to another aspect of the present invention, the light-blocking photosensitive resin composition is applied, and

[0028] A method for forming a pattern can be provided, comprising positionally exposing a coated light-blocking photosensitive resin composition to light and then developing it. Effects of the invention

[0029] According to the present invention, a light-blocking photosensitive resin composition comprising a polysilsesquioxane-based binder having developability in an alkaline aqueous solution can be provided by introducing an acid functional group, such as a carboxyl group, into the polysilsesquioxane structure.

[0030] In addition, a light-shielding photosensitive resin composition containing a polysilsesquioxane binder can be provided, which has excellent chemical resistance, does not degrade in light-shielding performance or deform the film during the OLED process, and has excellent adhesion. Specific details for implementing the invention

[0031] The present invention will be described below.

[0032] All terms used in this specification (including technical and scientific terms) may be used in a meaning commonly understood by those skilled in the art to which the present invention pertains, unless otherwise defined. Additionally, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0033] Furthermore, throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0036] As an embodiment of the present invention, a light-blocking photosensitive resin composition may comprise a binder, a pigment dispersion, a polyfunctional monomer, a photoinitiator, and a solvent. The binder may comprise a polysilsesquioxane-based binder.

[0037] Polysilsesquioxane-based binders are polysilsesquioxane compounds, which can be prepared by polymerizing silane monomers with compounds containing double bonds. For example, RSiO 3 / 2 Silane compounds containing units, RSiO 4 / 2 It can be prepared by copolymerizing a silane compound containing a unit and a compound containing a double bond, preferably RSiO 3 / 2 Two or more silane compounds containing units, RSiO 4 / 2 It can be prepared by polymerizing one or more silane compounds containing units and a compound containing double bonds. The silane monomer may include alkoxy groups, oxime groups, acetoxy groups, etc., but is not limited thereto as long as it can form polysilsesquioxane by hydrolysis dehydration condensation reaction. The R is a monovalent hydrocarbon group and may independently be an alkyl group such as methyl, ethyl, or propyl; an alkenyl group such as vinyl, allyl, isopropenyl, butenyl, hexenyl, and cycloalkenyl groups; an aryl group such as phenyl or xylyl; an aralkyl group such as benzyl; or an alkyl halide group.

[0038] RSiO 3 / 2 Examples of silane compounds containing the unit include, but are not limited to, methyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0039] RSiO 4 / 2 Examples of silane compounds containing the unit include, but are not limited to, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentoxysilane, etc.

[0040] Polysilsesquioxane-based binders may contain double bonds by polymerizing a compound containing double bonds, and the double bonds may originate from ester compounds, methacryloxy group-containing compounds, acryloxy group-containing compounds, methacrylic group-containing compounds, acrylic group-containing compounds, carboxylic acid compounds, sulfinyl compounds, or sulfonyl compounds. Preferably, the double bonds may originate from ester compounds, methacryloxy group-containing compounds, acryloxy group-containing compounds, methacrylic group-containing compounds, or acrylic group-containing compounds.

[0041] Compounds containing double bonds are, for example, ester compounds, methacrylic oxygen group-containing compounds, acrylic oxygen group-containing compounds, methacrylic group-containing compounds, acrylic group-containing compounds, carboxylic acid compounds, sulfinyl compounds, or sulfonyl compounds, and may include compounds containing double bonds included in -C(=O)O-, -C(=O)-, -C(=O)OH, -S(=0)-, or -S(=0)(=0)-. These double bonds may remain in the polysilsesquioxane-based binder even after polymerization.

[0042] Polysilsesquioxane-based binders can be polymerized by further including a compound containing an acid functional group. By polymerizing by further including a compound containing an acid functional group, the structure of the polysilsesquioxane-based binder may further include an acid functional group. The acid functional group may be derived from a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound, and specifically may include a carboxyl group, a sulfinic acid group, a sulfonic acid group, etc.

[0043] When polymerizing a polysilsesquioxane-based binder from a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound, it may include both an acid functional group and a double bond.

[0044] Polysilsesquioxane-based binders can have improved chemical resistance when double bonds are introduced into the binder structure, and improved developability in alkaline aqueous solutions when acid functional groups are introduced.

[0045] Preferably, a carboxylic acid compound may be used as a compound containing an acid functional group. To introduce an acid functional group into the structure of a polysilsesquioxane-based binder, a succinic acid compound, for example, an anhydrous succinic acid compound may be used. As an anhydrous succinic acid compound, triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, etc. may be used, but are not limited thereto. With the introduction of the acid functional group, the acid value of the polysilsesquioxane-based binder may be about 5 to 30 mgKOH / g, preferably about 5 to 25 mgKOH / g, and more preferably about 10 to 20 mgKOH / g.

[0046] A polysilsesquioxane-based binder can be prepared, for example, by mixing two or more silane monomers and a compound containing a double bond, reacting the mixture with an aqueous hydrochloric acid solution, and then stirring the reaction mixture. Alternatively, it can be prepared by mixing two or more silane monomers, a compound containing an acid functional group, and a compound containing a double bond, reacting the mixture with an aqueous hydrochloric acid solution, and then stirring the reaction mixture. Subsequently, the polysilsesquioxane-based binder can be obtained by washing and purifying. The silane monomer is RSiO 3 / 2 Silane compounds containing units and RSiO 4 / 2 Silane compounds containing units can be used.

[0047] When silane monomers, compounds containing acid functional groups, and compounds containing double bonds are referred to as monomers for polymerizing polysilsesquioxane-based binders, the mole fraction of a compound capable of introducing one double bond per molecule into a polysilsesquioxane-based binder is about 0.1 to 0.5, preferably about 0.2 to 0.5, and more preferably about 0.2 to 0.45, although this may vary depending on the number of double bonds per molecule included in the compound containing double bonds.

[0048] Polysilsesquioxane-based binders can be polymerized from a silane monomer and a compound containing a double bond; from a silane monomer and a compound containing an acid functional group; from a silane monomer, a compound containing a double bond and a compound containing an acid functional group; or from a silane monomer and a compound containing both a double bond and an acid functional group.

[0050] The pigment dispersion may include a pigment, a dispersant, and a dispersion solvent.

[0051] The dispersant may have an acid value within a certain range, an amine value, or both an acid value and an amine value. When it has an acid value and an amine value within a certain range, the dispersibility of the pigment dispersion is good, the compatibility between the binder and the dispersant is excellent, and at the same time, the developability of the photosensitive resin composition containing the pigment dispersion can be excellent.

[0052] Dispersants may be fatty acid-based, phosphate-based, carboxylic acid-based, polyurethane-based, polyamine-based, polyacrylate-based, polyacrylic-based compounds or structured copolymer compounds, and appropriate functional groups may be introduced into fatty acid-based, phosphate-based, carboxylic acid-based, polyurethane-based, polyamine-based, polyacrylate-based, polyacrylic-based compounds or structured copolymer compounds to have an acid value, an amine value, or both an acid value and an amine value.

[0053] For example, BYK’s DISPERSEBYK 163, 168, 170, 174, 182, 9133, 9076, 2150, 2151, 2152, 2159, 181, 187, 190, 191 or BYKJET 9131, 2000, 2001 may be used as a dispersant, but are not limited thereto.

[0054] Pigments such as black pigments, red pigments, blue pigments, green pigments, and yellow pigments may be used, but are not particularly limited thereto. For example, black pigments may be used alone, in which case the light-blocking properties of the photosensitive resin composition are excellent. Preferably, one or more pigments selected from the group consisting of red pigments, blue pigments, green pigments, yellow pigments, etc., may be mixed with black pigments and used, in which case the problem of internal incomplete curing of the photosensitive resin composition that may occur when black pigments are used alone can be resolved.

[0055] Black pigments may be used, for example, aniline black, titanium black, carbon black, lactam black, etc., but are not limited thereto. When using a black pigment alone, lactam black may be used, and since it has high light transmittance in the ultraviolet region of 350 to 400 nm, the photoinitiator can efficiently initiate the reaction.

[0056] For the red pigment, CI Pigment Red 177, CI Pigment Red 254, or derivatives thereof may be used; for the blue pigment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, and 64 may be used; for the green pigment, CI Pigment Green 6, 7, 10, 36, 37, 58, 59, 62, and 63 may be used; and for the yellow pigment, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, etc. may be used, but are not limited thereto.

[0057] The dispersion solvent may be an organic solvent, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, diethyl oxylates, and diethyl malonate; Dicarboxylates of glycols, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxypropionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, e.g., methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, diacetone alcohol methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; It may be one or more selected from the group consisting of ketal or acetal, 1,3-dioxalan and diethoxypropane; lactone, butyrolactone and gamma valerolactone; amide derivative, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof.

[0058] The pigment dispersion liquid may comprise 3 to 30 parts by weight of the pigment, 1 to 10 parts by weight of the dispersant, and 20 to 200 parts by weight of a dispersion solvent, preferably 8 to 25 parts by weight of the pigment, 2 to 8 parts by weight of the dispersant, and 40 to 160 parts by weight of a dispersion solvent, and more preferably 10 to 20 parts by weight of the pigment, 3 to 6 parts by weight of the dispersant, and 60 to 120 parts by weight of a dispersion solvent.

[0059] A pigment dispersion can be prepared by introducing a pigment, a dispersant, and a dispersion solvent into a dispersion device and dispersing them until they reach a particle size (D50) within a certain range. The dispersion device is not particularly limited. For example, a pigment, a dispersant, and a dispersion solvent can be introduced into a horizontal bead mill, 0.1 mm beads are added, and the pigment dispersion can be prepared by dispersing them until the particle size (D50) of the pigment dispersion reaches 5 to 100 nm.

[0061] Polyfunctional monomers may be used to increase reactivity to ultraviolet light, such as monomers with four or more functions. For example, Dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, and pentaerythritol ethoxylated tetraacrylate may be used.

[0062] Examples of photoinitiators include 1-[4-(phenylthio)phenyl]-1,2-octanedion 2-(O-benzoyloxime), benzoin, 1-hydroxy-cyclohexyl-phenyl ketone, α,α-dimethoxy-α-hydroxyacetophenone, 1-(4-isopropylenyl)-2-hydroxy-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]-propanone, methyldiethanolamine, triethanolamine, etc.

[0063] The solvent may be an organic solvent, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, diethyl oxylates, and diethyl malonate; Dicarboxylates of glycols, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxypropionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, e.g., methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, diacetone alcohol methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; It may be one or more selected from the group consisting of ketal or acetal, 1,3-dioxalan and diethoxypropane; lactone, butyrolactone and gamma valerolactone; amide derivative, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof.

[0065] As an embodiment according to the present invention, a light-shielding photosensitive resin composition may comprise 10 to 30 parts by weight of a binder, 40 to 60 parts by weight of a pigment dispersion, 1 to 20 parts by weight of a polyfunctional monomer, 0.1 to 5 parts by weight of a photoinitiator, and 10 to 30 parts by weight of a solvent. Preferably, it may comprise 10 to 25 parts by weight of a binder, 45 to 60 parts by weight of a pigment dispersion, 5 to 20 parts by weight of a polyfunctional monomer, 1 to 5 parts by weight of a photoinitiator, and 10 to 25 parts by weight of a solvent, and more preferably, it may comprise 15 to 25 parts by weight of a binder, 45 to 55 parts by weight of a pigment dispersion, 5 to 15 parts by weight of a polyfunctional monomer, 2 to 5 parts by weight of a photoinitiator, and 15 to 25 parts by weight of a solvent.

[0067] As an embodiment of the present invention, a cured product can be prepared by curing the light-shielding photosensitive resin composition. The curing of the light-shielding photosensitive resin composition can be achieved, for example, by using lactam black as a black pigment, by irradiating ultraviolet light of 350 to 400 nm, which is a region where the light transmittance of lactam black is high, and at this time, a photoinitiator that initiates an initiation reaction in the 350 to 400 nm ultraviolet region can be selected and used.

[0068] As an embodiment of the present invention, a method for forming a pattern may include applying the light-blocking photosensitive resin composition, selectively exposing the applied light-blocking photosensitive resin composition to light, and then developing. Specifically, selective exposure to light may be performed by using a photomask having a desired pattern formed thereon to process the exposed portion and the unexposed portion so that they are distinguished.

[0070] The present invention has been described in detail below with reference to the embodiments and comparative examples of the present invention.

[0072] Synthesis Example 1. Synthesis of Polysilsesquioxane Copolymer

[0073] 39 parts by weight of methyltrimethoxysilane, 105 parts by weight of phenyltrimethoxysilane, 60 parts by weight of tetraethoxysilane, 71 parts by weight of methacryloxypropyltrimethoxysilane, and 13 parts by weight of triethoxysilylpropyl succinic anhydride were added to a 500 ml three-necked round-bottom flask and stirred at room temperature for 10 minutes. Subsequently, 200 g of an aqueous hydrochloric acid solution dissolved at 5% in deionized water was slowly added dropwise at a reaction temperature of 50°C or lower to allow the reaction to proceed. After stirring the reaction mixture for 10 minutes, the temperature was raised to 80°C to polymerize the silsesquioxane copolymer. After washing and purifying with deionized water and ethyl acetate, unreacted materials and impurities were removed by vacuum distillation. Subsequently, PGMEA was added to obtain a silsesquioxane copolymer with a solid content of 50%.

[0075] Synthesis Examples 2 to 6. Synthesis of Polysilsesquioxane Copolymers

[0076] Polysilsesquioxane copolymers of Synthesis Examples 2 to 6 were obtained by preparing them in the same manner as Synthesis Example 1, but varying the weight parts of methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride mixed. The weight ratios of methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride used in each are shown in Table 1.

[0077]

[0079] Preparation Example 1. Preparation of pigment dispersion solution

[0080] 15 parts by weight of lactam black as pigment, 4.5 parts by weight of dispersant (DISPERSEBYK 163), and 80.5 parts by weight of PGMEA as dispersion solvent were added to a horizontal bead mill, and 0.1 mm beads were added and dispersed until the particle size (D50) of the pigment dispersion became 50 nm.

[0082] Example 1. Preparation of a light-blocking photosensitive resin composition

[0083] A resin composition of Example 1 was prepared by mixing 20 parts by weight of the polysilsesquioxane-based binder of Synthesis Example 1, 50 parts by weight of the pigment dispersion of Preparation Example 1, 10 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, 3 parts by weight of a photoinitiator (OXE-01), and 17 parts by weight of PGMEA as a solvent.

[0084] The resin compositions of Example 2 and Comparative Examples 1 to 4 were prepared in the same manner as Example 1, but using the polysilsesquioxane-based binders of Synthesis Examples 2 to 6, respectively.

[0086] Experimental Example 1. Evaluation of the light-blocking properties of a light-blocking photosensitive resin composition

[0087] Each of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4 was spin-coated onto an ITO substrate, and then soft baking was performed using a hot plate at approximately 110°C for about 70 seconds. After soft baking, the samples were exposed to approximately 90 mJ using an exposure device and then developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for about 70 seconds. Subsequently, hard baking was performed in an oven at 250°C for 1 hour to form a photosensitive resin film specimen with a thickness of 1 μm. The initial optical density (OD) at 550 nm was measured for the obtained photosensitive resin film specimen using a UV-visible spectrophotometer. The initial OD was measured to be approximately 1.5.

[0088] The hard-baked specimens were immersed in an acidic solvent prepared by stirring 10 parts by weight of 60% nitric acid, 70 parts by weight of 85% phosphoric acid, and 20 parts by weight of 99% acetic acid at 50°C for 150 seconds, then washed with water, and the final OD at 550 nm was measured. The light-blocking properties of each specimen were evaluated according to the following criteria and are shown in Table 2.

[0089] - ○ (Good): At 550nm, the final OD decreased to a range of 5% or less compared to the initial OD.

[0090] - △ (Normal): At 550nm, the final OD is reduced in the range of more than 10% to less than 20% compared to the initial OD.

[0091] - X (Defective): At 550nm, the final OD decreased by more than 20% compared to the initial OD.

[0093] Experimental Example 2. Evaluation of film deformation of a light-shielding photosensitive resin composition

[0094] A photosensitive resin film specimen with a thickness of 1 μm was formed using the same method as in Experimental Example 1. The initial thickness was measured using a contact-type thickness gauge (Alpha-step, 2D surface profiler).

[0095] The hard-baked specimens were immersed in an acidic solvent prepared by stirring 10 parts by weight of 60% nitric acid, 70 parts by weight of 85% phosphoric acid, and 20 parts by weight of 99% acetic acid at 50°C for 150 seconds, then washed with water, and the final thickness was measured. The film deformation of each specimen was evaluated according to the following criteria and is shown in Table 2.

[0096] - ○ (Good): The final thickness differs from the initial thickness by 5% or less.

[0097] - △ (Normal): The final thickness differs from the initial thickness by more than 5% and less than 7%.

[0098] - X (Defective): The final thickness differs from the initial thickness by more than 7%.

[0100] Experimental Example 3. Evaluation of Adhesion Strength of Light-Shielding Photosensitive Resin Composition

[0101] Photosensitive resin film specimens with a thickness of 1 μm were formed using the same method as in Experimental Example 1. The hard-baked specimens were prepared by immersing them in an acidic solvent prepared by stirring 10 parts by weight of 60% nitric acid, 70 parts by weight of 85% phosphoric acid, and 20 parts by weight of 99% acetic acid at 50°C for 150 seconds, followed by rinsing with water. By the method according to ASTM D3359 (cross-cut test), the surface of each specimen was cut into a right-angle grid pattern, and the degree of detachment from each specimen was checked. The adhesion strength of each specimen was evaluated according to the following criteria and is shown in Table 2.

[0102] - ○ (Good): 5B

[0103] - △ (Normal): 4B to 3B

[0104] - X (Defective): 2B to 0B

[0106] Experimental Example 4. Evaluation of Pattern Resolution (Developability) of Photosensitive Resin Composition

[0107] Each of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4 was spin-coated onto an ITO substrate, and then soft baking was performed using a hot plate at approximately 110°C for about 70 seconds. After soft baking, the exposed and unexposed areas were distinguished using a photomask with a pattern on the film, and then exposed to approximately 90 mJ using an exposure device, followed by development in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for about 70 seconds. Subsequently, hard baking was performed in an oven at 250°C for 1 hour to form a photosensitive resin film specimen with a thickness of 1 μm. The specimen subjected to hard baking was prepared by immersing it in an acidic solvent prepared by stirring 10 parts by weight of 60% nitric acid, 70 parts by weight of 85% phosphoric acid, and 20 parts by weight of 99% acetic acid at 50°C for 150 seconds, followed by rinsing with water.

[0108] Using FE-SEM, the developmental properties of each specimen were evaluated according to the following criteria and are shown in Table 2.

[0109] - ○ (Good): Minimum size 5μm or less

[0110] - △ (Normal): Minimum size greater than 5μm and less than 10μm

[0111] - X (Defective): Minimum size of 10μm or larger

[0113]

[0114] When combining the results of Experimental Examples 1 to 4, the resin compositions of Examples 1 to 4 all exhibited excellent adhesion, and the resin compositions of Examples 3 and 4 exhibited excellent light-blocking properties and very little variation in film thickness. In addition, in the case of Examples 1 and 4, acid functional groups were introduced, which also improved the pattern resolution.

[0115] On the other hand, Comparative Example 1 contained an excess amount of methacryloxypropyl trimethoxysilane containing a methacryloxy group, so it was excellent in terms of chemical resistance, but it did not contain triethoxysilylpropyl succinic anhydride, so the pattern resolution was found to be very poor. In the case of Comparative Example 2, the content of methacryloxypropyl trimethoxysilane was low, so it was evaluated as average to poor in terms of chemical resistance, and like Comparative Example 1, the pattern resolution was found to be very poor.

[0117] It is obvious to those skilled in the art that the present invention is not limited to the above embodiments and can be implemented with various modifications or variations within the scope of the technical essence of the present invention.

Claims

Claim 1 It comprises a binder, a pigment dispersion, a polyfunctional monomer, a photoinitiator, and a solvent, wherein the binder comprises a polysilsesquioxane-based binder, and the polysilsesquioxane-based binder is RSiO 3 / 2 A silane compound containing a unit (where R is a monovalent hydrocarbon group), RSiO 4 / 2 A light-shielding photosensitive resin composition prepared by polymerizing a silane compound containing a unit (where R is a monovalent hydrocarbon group), a methacryloxy group-containing compound, and a succinic anhydride compound, wherein the polysilsesquioxane-based binder comprises an acid functional group and a double bond, and the polysilsesquioxane-based binder has an acid value of 10 to 20 mgKOH / g. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 A light-shielding photosensitive resin composition according to claim 1, wherein the binder comprises 10 to 30 parts by weight; the pigment dispersion comprises 40 to 60 parts by weight; the polyfunctional monomer comprises 1 to 20 parts by weight; the photoinitiator comprises 0.1 to 5 parts by weight; and the solvent comprises 10 to 30 parts by weight. Claim 8 A light-blocking photosensitive resin composition according to claim 1, wherein the anhydrous succinic acid compound is triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride, or trimethoxysilylbutyl succinic anhydride. Claim 9 A light-shielding photosensitive resin composition according to claim 1, wherein the change in optical density (OD) before and after immersion of the film formed from the light-shielding photosensitive resin composition in an acidic solvent is less than 20%. Claim 10 A light-shielding photosensitive resin composition according to claim 1, wherein, after immersing the film formed from the light-shielding photosensitive resin composition in an acidic solvent, the adhesion strength according to ASTM D3359 is 5B to 3B. Claim 11 A light-shielding photosensitive resin composition according to claim 1, wherein the change in film thickness before and after immersion of the film formed from the light-shielding photosensitive resin composition in an acidic solvent is less than 7%. Claim 12 A light-shielding photosensitive resin composition according to claim 1, wherein the minimum size of the pattern produced by the light-shielding photosensitive resin composition is less than 10 μm. Claim 13 A cured product manufactured by curing a light-shielding photosensitive resin composition of any one of claims 1 and 7 to 12. Claim 14 A method for forming a pattern, comprising applying a light-shielding photosensitive resin composition according to any one of claims 1 and 7 to 12, positionally exposing the applied light-shielding photosensitive resin composition to light, and then developing.

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