Light-shielding photosensitive resin composition, cured product thereof, method for forming pattern, and method for preparing 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 preparing the photosensitive resin composition and, particularly, to a light-shielding photosensitive resin composition, a cured product thereof, a method for forming a pattern, and a method for preparing a photosensitive resin composition, in which the light-shielding photosensitive resin composition includes a polysilsesquioxane binder, and thus has excellent chemical resistance, does not undergo a reduction in light-shielding properties, and does not cause deformation of the coating in OLED processes.

Description

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

[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 producing a light-shielding photosensitive resin composition, and more particularly, to a light-shielding photosensitive resin composition comprising a polysilsesquioxane binder, which has excellent chemical resistance, does not deteriorate light-shielding properties in an OLED process, and does not cause deformation of a coating film, a cured product thereof, a method for forming a pattern, and a method for producing a light-shielding photosensitive resin composition.

[0002] Traditionally, OLED pixels have been patterned using methods such as screen printing, roll-to-roll, and laser direct patterning. Additionally, photolithography using a photoresist composition is now being used in the patterning process of OLED display manufacturing. Photolithography enables large-area patterning of OLED pixels, and can also pattern ultra-fine OLED pixels, enabling the implementation of high-resolution display screens.

[0003] To realize high-density, ultra-high-resolution OLED display screens, forming ultra-fine patterns remains crucial. Methods for forming ultra-fine patterns include positive and negative methods. Positive methods involve removing the exposed portion of a photoresist composition to form a pattern, while negative methods involve removing the unexposed portion of the photoresist composition to form a pattern.

[0004] The photoresist compositions used in both positive and negative methods are distinct. Among these, the negative photoresist composition must have developability so that the unexposed portion can be removed. Conventional negative photoresist photosensitive resin compositions contain acid functional groups in the binder, and thus development is performed using an alkaline developer such as KOH or TMAH (Tetramethyl Ammonium Hydroxide). Negative photosensitive resin compositions with improved developability have been disclosed, for example, in Korean Patent No. 10-2585445 (October 5, 2023), Korean Patent No. 10-1787651 (October 18, 2017), and Korean Patent No. 10-1306778 (September 17, 2013).

[0005] The negative photosensitive resin composition may contain an alkali-soluble resin or binder to enable removal of unexposed portions. Examples of binders proposed include acrylic resins, polyimide resins, phenol resins, polyurethane resins, polyester resins, polyvinyl alcohol resins, and epoxy resins.

[0006] In addition, polysilsesquioxane binders are copolymers of polysiloxanes, and have excellent chemical resistance, making them suitable for use in photosensitive resin compositions. However, since polysilsesquioxane is synthesized through a sol-gel reaction using an acid / base catalyst, it has been difficult to introduce acid functional groups into the binder itself, as is the case with conventional binders. As a result, most polysilsesquioxane binders do not dissolve well in alkaline developers, resulting in poor developability. Despite the above-mentioned physical properties of polysilsesquioxane binders, their application to negative-type photosensitive resin compositions is currently difficult.

[0007] Accordingly, the present invention sought to provide a polysilsesquioxane binder having developability for an alkaline aqueous solution by controlling acid functional groups and double bonds within the polysilsesquioxane structure, and a light-shielding photosensitive resin composition comprising the same.

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

[0009] The above binder includes a polysilsesquioxane binder,

[0010] The above polysilsesquioxane-based binder can provide a light-blocking photosensitive resin composition containing a double bond.

[0011] Preferably, a light-shielding photosensitive resin composition can be provided in which the double bond is derived from an ester compound, a methacryloxy group-containing compound, an acryloxy group-containing compound, a methacryl 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 further comprising 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-shielding photosensitive resin composition can be provided in which the acid functional group is derived from a succinic acid compound.

[0015] Preferably, the light-shielding photosensitive resin composition can be provided in which the succinic acid compound is an anhydrous succinic acid compound.

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

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

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

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

[0020] The above solvent can provide a light-blocking photosensitive resin composition comprising 10 to 30 parts by weight.

[0021] Preferably, the succinic acid compound can provide a light-shielding photosensitive resin composition, wherein the light-shielding photosensitive resin composition is 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 a 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 above light-shielding photosensitive resin composition in an acidic solvent, a light-shielding photosensitive resin composition having an adhesive 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 a change in the thickness of a film formed from the light-shielding photosensitive resin composition before and after immersing the film 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 manufactured from the light-shielding photosensitive resin composition is less than 10 μm.

[0026] According to another aspect of the present invention, a cured product can be provided, which is manufactured by curing the above-described light-shielding photosensitive resin composition.

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

[0028] A method for forming a pattern can be provided, which includes selectively exposing a coated light-shielding photosensitive resin composition to light and then developing it.

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

[0030] In addition, a light-shielding photosensitive resin composition having excellent chemical resistance including a polysilsesquioxane binder, no decrease in light-shielding properties or deformation of a coating film in an OLED process, and excellent adhesive strength can be provided.

[0031] Hereinafter, the present invention will be described.

[0032] All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used in their common sense by those of ordinary skill in the art to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0033] Additionally, throughout this specification, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0034]

[0035] As one embodiment of the present invention, a light-shielding photosensitive resin composition may include a binder, a pigment dispersion, a multifunctional monomer, a photoinitiator, and a solvent. The binder may include a polysilsesquioxane-based binder.

[0036] Polysilsesquioxane binders are polysilsesquioxane compounds, which can be prepared by polymerizing a silane monomer and a compound containing a double bond. For example, polysilsesquioxane binders include RSiO 3 / 2 Silane compound capable of forming units, RSiO 4 / 2 It can be produced by copolymerizing a silane compound capable of forming a unit and a compound containing a double bond, preferably RSiO 3 / 2 Two or more silane compounds capable of forming a unit, RSiO 4 / 2 It can be manufactured by polymerizing one or more silane compounds capable of forming a unit and a compound containing a double bond. The silane monomer may include an alkoxy group, an oxime group, an acetoxy group, etc., but is not limited thereto as long as it can form polysilsesquioxane by a hydrolysis, dehydration, and condensation reaction. The R is a monovalent hydrocarbon group, and may be, for example, an alkyl group such as methyl, ethyl, or propyl independently; an alkenyl group such as vinyl, allyl, isopropenyl, butenyl, hexenyl, and cycloalkenyl; an aryl group such as phenyl or xylyl; an aralkyl group such as benzyl; or a halogenated alkyl group.

[0037] RSiO 3 / 2 Examples of silane compounds capable of forming the unit include, but are not limited to, methyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0038] RSiO 4 / 2 Examples of silane compounds capable of forming units include, but are not limited to, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrapentoxysilane.

[0039] The polysilsesquioxane binder may include a double bond in the molecule by polymerizing a compound containing a double bond, and the double bond may be derived from an ester compound, a methacryloxy group-containing compound, an acryloxy group-containing compound, a methacryl group-containing compound, an acryl group-containing compound, a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound. Preferably, the double bond may be derived from an ester compound, a methacryloxy group-containing compound, an acryloxy group-containing compound, a methacryl group-containing compound, or an acryl group-containing compound.

[0040] The compound containing a double bond is, for example, an ester compound, a methacryloxy group-containing compound, an acryloxy group-containing compound, a methacryl group-containing compound, an acryl group-containing compound, a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound, and may include a compound containing a double bond contained in -C(=O)O-, -C(=O)-, -C(=O)OH, -S(=0)-, or -S(=0)(=0)-. Such a double bond may remain in the polysilsesquioxane-based binder even after polymerization.

[0041] The polysilsesquioxane-based binder may be polymerized by further including a compound containing an acid functional group. By further including a compound containing an acid functional group and polymerizing the polysilsesquioxane-based binder, an acid functional group may be further included within the structure of the binder. 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, or the like.

[0042] When polymerizing a polysilsesquioxane binder from a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound, it may contain both an acid functional group and a double bond.

[0043]

[0044] Polysilsesquioxane binders can have improved chemical resistance when a double bond is introduced into the structure of the binder, and can have improved developability in an alkaline aqueous solution when an acid functional group is introduced.

[0045] As a compound containing an acid functional group, a carboxylic acid compound can be preferably used. In order to introduce an acid functional group into the structure of the polysilsesquioxane binder, a succinic acid compound, for example, a succinic anhydride compound, can be used. Examples of the succinic anhydride compound that can be used include, but are not limited to, triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride, and trimethoxysilylbutyl succinic anhydride. By introducing acid functional groups, the acid value of the polysilsesquioxane binder can 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 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 solution. 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 solution. Thereafter, the mixture can be washed and purified to obtain a polysilsesquioxane binder. The silane monomer is RSiO. 3 / 2 Silane compounds capable of forming units and / or RSiO 4 / 2Silane compounds capable of forming units can be used.

[0047] When a silane monomer, a compound containing an acid functional group, and a compound containing a double bond are referred to as monomers for polymerizing a polysilsesquioxane-based binder, the number of double bonds per molecule included in the compound containing a double bond may vary, but based on the entire monomer used for polymerizing the polysilsesquioxane-based binder, the mole fraction of a compound containing one double bond in the molecule is about 0.1 to 0.5, preferably about 0.2 to 0.5, and more preferably about 0.2 to 0.45.

[0048] The polysilsesquioxane binder can be polymerized from a compound including a silane monomer and a double bond; from a compound including a silane monomer and an acid functional group; from a silane monomer, a compound including a double bond, and a compound including an acid functional group; or from a silane monomer and a compound including both a double bond and an acid functional group.

[0049]

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

[0051] The dispersant may have a range of acid values, amine values, or both acid values ​​and amine values. When the dispersant has a range of acid values ​​and amine values, the pigment dispersion may have good dispersibility, excellent compatibility between the binder and the dispersant, and at the same time, the developability of the photosensitive resin composition containing the pigment dispersion may be improved.

[0052] Dispersants may be fatty acid-based, phosphoric acid-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, an appropriate functional group may be introduced into fatty acid-based, phosphoric acid-based, carboxylic acid-based, polyurethane-based, polyamine-based, polyacrylate-based, polyacrylic-based compounds, or structured copolymer compounds.

[0053] Dispersants that can be used include, but are not limited to, DISPERSEBYK 163, 168, 170, 174, 182, 9133, 9076, 2150, 2151, 2152, 2159, 181, 187, 190, 191, or BYKJET 9131, 2000, 2001 from BYK.

[0054] The pigment may be a black pigment, a red pigment, a blue pigment, a green pigment, a yellow pigment, etc., and is not particularly limited thereto. For example, a black pigment 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 a red pigment, a blue pigment, a green pigment, a yellow pigment, etc. may be mixed with a black pigment and used, and in this case, the problem of internal non-curing of the photosensitive resin composition that may occur when a black pigment is used alone can be resolved.

[0055] Examples of black pigments that can be used include, but are not limited to, aniline black, titanium black, carbon black, and lactam black. When using a black pigment alone, lactam black can be used, and its high light transmittance in the 350 to 400 nm ultraviolet range allows the photoinitiator to efficiently initiate the reaction.

[0056] The red pigment may be CI Pigment Red 177, CI Pigment Red 254, or derivatives thereof, the blue pigment may be CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, and 64, the green pigment may be CI Pigment Green 6, 7, 10, 36, 37, 58, 59, 62, and 63, the yellow pigment may be 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, You can use 37, 37:1, 40, etc., but are not limited to these.

[0057] The dispersion solvent may be an organic solvent, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, 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, diethylene glycol dimethyl ether, glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), carboxylate, ethyl acetate, n-butyl acetate, amyl acetate, carboxylate of dibasic acid, diethyl oxylate, diethyl malonate, dicarboxylate of glycol, ethylene glycol diacetate, propylene glycol Diacetate, hydroxycarboxylate, methyl lactate, ethyl lactate, ethyl glycolate, ethyl-3-hydroxypropionate, ketone ester, methyl pyruvate, ethyl pyruvate, alkoxycarboxylic acid ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl ethoxypropionate, ketone derivatives, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, 2-heptanone, ketone ether derivatives, diacetone alcohol methyl ether, ketone alcohol derivatives, acetol, diacetone alcohol, ketal, acetal, 1,3-dioxalane, diethoxypropane, lactone, butyrolactone, gamma valerolactone, amide derivatives, It may be at least one selected from the group consisting of dimethylacetamide, dimethylformamide, anisole, and mixtures thereof.

[0058] The pigment dispersion may contain 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 the 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 the 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 the dispersion solvent.

[0059] Pigment dispersions can be manufactured by placing pigment, dispersant, and dispersion solvent into a dispersion device and dispersing the pigment until it reaches a particle size (D50) of a certain range. The dispersion device is not particularly limited. For example, the pigment, dispersant, and dispersion solvent can be placed into a horizontal bead mill, 0.1 mm beads can be added, and the pigment dispersion can be manufactured by dispersing the pigment until the particle size (D50) of the pigment dispersion reaches 5 to 100 nm.

[0060]

[0061] The polyfunctional monomer may be a polyfunctional monomer having four or more functional groups to increase reactivity to ultraviolet rays. For example, at least one selected from the group consisting of dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, and pentaerythritol ethoxylated tetraacrylate may be used.

[0062] Photoinitiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), benzoin, 1-hydroxy-cyclohexyl-phenyl ketone, α,α-dimethoxy-α-hydroxy acetophenone, 1-(4-isopropylenyl)-2-hydroxy-2-methyl-propan-1-one, 1-[4-(2hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]-propanone, methyldiethanolamine, and triethanolamine.

[0063] The solvent may be an organic solvent, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, 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, diethylene glycol dimethyl ether, glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), carboxylate, ethyl acetate, n-butyl acetate, amyl acetate, carboxylate of dibasic acid, diethyl oxylate, diethyl malonate, dicarboxylate of glycol, ethylene glycol diacetate, propylene glycol Diacetate, hydroxycarboxylate, methyl lactate, ethyl lactate, ethyl glycolate, ethyl-3-hydroxypropionate, ketone ester, methyl pyruvate, ethyl pyruvate, alkoxycarboxylic acid ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl ethoxypropionate, ketone derivatives, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, 2-heptanone, ketone ether derivatives, diacetone alcohol methyl ether, ketone alcohol derivatives, acetol, diacetone alcohol, ketal, acetal, 1,3-dioxalane and diethoxypropane, lactone, butyrolactone, gamma valerolactone, amide derivatives, It may be at least one selected from the group consisting of dimethylacetamide, dimethylformamide, anisole, and mixtures thereof.

[0064]

[0065] As an embodiment of the present invention, the light-shielding photosensitive resin composition may include 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 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 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.

[0066]

[0067] As one embodiment of the present invention, a cured product can be manufactured by curing the light-shielding photosensitive resin composition. For example, when lactam black is used as a black pigment, curing of the light-shielding photosensitive resin composition can be accomplished by irradiating it with ultraviolet rays in the range of 350 to 400 nm, which is a range in which lactam black has high light transmittance. At this time, a photoinitiator that initiates the reaction in the range of 350 to 400 nm ultraviolet rays can be selected and used.

[0068] As one embodiment of the present invention, a method for forming a pattern may include applying the light-shielding photosensitive resin composition, selectively exposing the applied light-shielding photosensitive resin composition to light, and then developing the composition. Specifically, the selective exposure to light may be performed by using a photomask having a desired pattern formed thereon to distinguish between exposed and unexposed areas.

[0069] Hereinafter, the present invention is specifically described with reference to examples and comparative examples of the present invention.

[0070]

[0071] Synthesis Example 1. Synthesis of polysilsesquioxane binder

[0072] In a 500 ml three-necked round-bottomed flask, 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 and stirred at room temperature for 10 minutes. Then, 200 g of a 5% hydrochloric acid aqueous solution dissolved in deionized water was slowly added dropwise at a reaction temperature of 50°C or lower and reacted. After stirring the reaction solution for 10 minutes, the temperature was increased to 80°C to polymerize a polysilsesquioxane binder. After washing and purifying with deionized water and ethyl acetate, unreacted materials and impurities were removed by distillation under reduced pressure. Thereafter, PGMEA was added to obtain a polysilsesquioxane binder having a solid content of 50%.

[0073]

[0074] Synthesis Examples 2 to 6. Synthesis of polysilsesquioxane binders

[0075] Polysilsesquioxane binders of Synthetic Examples 2 to 6 were obtained in the same manner as in Synthetic Example 1, except that the weight parts of methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride were mixed differently. The weight ratios of methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride used in each are shown in Table 1.

[0076]

[0077] Synthesis Example Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Methyltrimethoxysilane 392550058 Phenyltrimethoxysilane 10510510510585114 Tetraethoxysilane 606060606060 Methacryloxypropyltrimethoxysilane 7110714314317835 Triethoxysilylpropyl succinic anhydride 13001300 Physical properties Acid value (mgKOH / g) 11001600

[0078]

[0079] Manufacturing Example 1. Manufacturing of pigment dispersion

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

[0081]

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

[0083] A resin composition of Example 1 was prepared by mixing 20 parts by weight of the polysilsesquioxane 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 multifunctional monomer, 3 parts by weight of a photoinitiator (OXE-01), and 17 parts by weight of PGMEA as a solvent.

[0084]

[0085] Examples 2 to 4 and Comparative Examples 1 to 2. Preparation of a light-shielding photosensitive resin composition

[0086] The resin compositions of Examples 2 to 4 and Comparative Examples 1 to 2 were manufactured in the same manner as in Example 1, but the polysilsesquioxane binder of Synthesis Example 1 was replaced with the polysilsesquioxane binder of Synthesis Example 2 to 6, respectively.

[0087]

[0088] Experimental Example 1. Evaluation of the light-shielding properties of a light-shielding photosensitive resin composition.

[0089] Each of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 was spin-coated on an ITO substrate, and then soft-baked using a hot plate at about 110°C for about 70 seconds. After soft-baking, the resulting composition was exposed to about 90 mJ of light 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. Thereafter, hard-baking was performed in an oven at 250°C for 1 hour to form a photosensitive resin film specimen having a thickness of 1 μm. The initial OD (Optical Density) at 550 nm of the obtained photosensitive resin film specimen was measured using a UV-visible spectrophotometer. The initial OD was measured to be about 1.5.

[0090] The hard-baked specimens were immersed in an acidic solvent prepared by mixing 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-shielding properties of each specimen were evaluated according to the following criteria, which are shown in Table 2.

[0091] - ○ (Good): At 550 nm, the final OD is reduced by less than 5% compared to the initial OD.

[0092] - △ (Normal): At 550 nm, the final OD is reduced by 10% or more to 20% or less than the initial OD.

[0093] - X (Defective): Final OD at 550 nm is reduced by more than 20% compared to the initial OD.

[0094]

[0095] Experimental Example 2. Evaluation of film deformation of a light-shielding photosensitive resin composition.

[0096] 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 thickness measuring device (Alpha-step, 2D surface profiler).

[0097] The hard-baked specimens were immersed in an acidic solvent prepared by mixing 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 based on the following criteria, and is shown in Table 2.

[0098] - ○ (Good): The final thickness differs by less than 5% from the initial thickness.

[0099] - △ (Normal): The final thickness differs from the initial thickness by more than 5% but less than 7%.

[0100] - X (Defective): The final thickness differs by more than 7% from the initial thickness.

[0101]

[0102] Experimental Example 3. Evaluation of Adhesion of a Photosensitive Resin Composition with Light-Screening Properties

[0103] Photosensitive resin film specimens with a thickness of 1 μm were formed using the same method as Experimental Example 1. 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, and then washed with water. According to the method (cross-cut test) according to ASTM D3359, the surface of each specimen was cut into a right-angled grid pattern, and the degree of separation from each specimen was confirmed. The adhesive strength of each specimen was evaluated according to the following criteria, which are shown in Table 2.

[0104] - ○ (Good): 5B

[0105] - △ (Normal): 4B to 3B

[0106] - X (bad): 2B to 0B

[0107]

[0108] Experimental Example 4. Evaluation of Pattern Resolution (Developability) of Photosensitive Resin Compositions

[0109] Each of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 was spin-coated on an ITO substrate, and then soft-baked using a hot plate at about 110°C for about 70 seconds. After soft-baking, the coating film was exposed / unexposed using a patterned photomask, and then exposed at about 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. After that, hard-baking was performed in an oven at 250°C for 1 hour to form a photosensitive resin coating film specimen having a thickness of 1 μm. The hard-baked specimen was 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, and then rinsed with water to prepare.

[0110] Using FE-SEM, the development properties of each specimen were evaluated based on the following criteria, and are shown in Table 2.

[0111] - ○ (Good): Minimum size is 5 μm or less

[0112] - △ (Normal): Minimum size is more than 5 μm but less than 10 μm

[0113] - X (defective): Minimum size is 10μm or more

[0114]

[0115] Classification Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Binder Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Chemical resistance Light shielding property △△○○○× Film thickness change △△○○○△ Adhesive strength ○○○○○△ Pattern resolution ○△△○××

[0116]

[0117] When the results of Experimental Examples 1 to 4 are summarized, the resin compositions of Examples 1 to 4 all exhibited excellent adhesive strength, and the resin compositions of Examples 3 and 4 exhibited excellent light-blocking properties and very little change in film thickness. In addition, in the case of Examples 1 and 4, the introduction of acid functional groups also improved the pattern resolution.

[0118] On the other hand, in the case of Comparative Example 1, since it contained an excessive amount of methacryloxypropyl trimethoxysilane containing a methacryloxy group, it was excellent in terms of chemical resistance, but since it did not contain triethoxysilylpropyl succinic anhydride, it was found that the pattern resolution was very poor. In the case of Comparative Example 2, since the content of methacryloxypropyl trimethoxysilane was small, it was evaluated as average to poor in terms of chemical resistance, and like Comparative Example 1, it was found that the pattern resolution was very poor.

[0119]

[0120] It is obvious to a person skilled in the art that the present invention is not limited to the above embodiments, and that various modifications or changes can be made without departing from the technical spirit of the present invention.

Claims

1. Containing a binder, a pigment dispersion, a multifunctional monomer, a photoinitiator and a solvent, The above binder comprises a polysilsesquioxane binder, A light-shielding photosensitive resin composition, wherein the polysilsesquioxane-based binder contains a double bond.

2. In claim 1, A light-shielding photosensitive resin composition, wherein the double bond is derived from an ester compound, a methacryloxy group-containing compound, an acryloxy group-containing compound, a methacryl group-containing compound, an acrylic group-containing compound, a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound.

3. In claim 1, A light-shielding photosensitive resin composition, wherein the polysilsesquioxane-based binder further contains an acid functional group.

4. In claim 3, A light-shielding photosensitive resin composition, wherein the acid functional group is derived from a carboxylic acid compound, a sulfinyl compound or a sulfonyl compound.

5. In claim 3, A light-shielding photosensitive resin composition, wherein the acid functional group is derived from a succinic acid compound.

6. In claim 5, A light-shielding photosensitive resin composition, wherein the above-mentioned succinic acid compound is an anhydrous succinic acid compound.

7. In claim 1, The above binder is 10 to 30 parts by weight; The pigment dispersion is 40 to 60 parts by weight; The above polyfunctional monomer is 1 to 20 parts by weight; The photoinitiator is 0.1 to 5 parts by weight; and A light-shielding photosensitive resin composition comprising 10 to 30 parts by weight of the solvent.

8. In claim 5, A light-shielding photosensitive resin composition, wherein the above succinic acid compound is triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride or trimethoxysilylbutyl succinic anhydride.

9. In claim 1, A light-shielding photosensitive resin composition, wherein a change in optical density (OD) before and after immersing a film formed from the light-shielding photosensitive resin composition in an acidic solvent is less than 20%.

10. In claim 1, A light-shielding photosensitive resin composition having an adhesive strength of 5B to 3B according to ASTM D3359 after immersing a film formed from the above light-shielding photosensitive resin composition in an acidic solvent.

11. In claim 1, A light-shielding photosensitive resin composition, wherein a change in the thickness of a coating film formed from the light-shielding photosensitive resin composition before and after immersing the coating film in an acidic solvent is less than 7%.

12. In claim 1, A light-shielding photosensitive resin composition, wherein the minimum size of a pattern manufactured from the light-shielding photosensitive resin composition is less than 10 μm.

13. A cured product manufactured by curing the light-shielding photosensitive resin composition of any one of claims 1 to 12.

14. Applying a light-shielding photosensitive resin composition of any one of claims 1 to 12, A method for forming a pattern, comprising selectively exposing a coated light-shielding photosensitive resin composition to light and then developing it.