Photosensitive resin composition, cured product thereof, method for forming pattern, and method for preparing photosensitive resin composition

Abstract

The present invention relates to a photosensitive resin composition, a cured product thereof, a method for forming a pattern, and a method for preparing a photosensitive resin composition. Specifically, the present invention relates to a photosensitive resin composition which contains a polysilsesquioxane binder and exhibits excellent storage stability, surface coating properties, and resolution, a cured product, a method for forming a pattern, and a method for preparing a photosensitive resin composition.

Description

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 photosensitive resin composition, a cured product thereof, a method for forming a pattern, and a method for producing a photosensitive resin composition, and more particularly, to a photosensitive resin composition comprising a polysilsesquioxane binder and having excellent storage stability, surface coatability, and resolution, a cured product thereof, a method for forming a pattern, and a method for producing a 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] Recently, the display industry has been focusing on OLED display devices, which display images through organic light-emitting layers that generate light independently, rather than through a backlight unit like a liquid crystal display (LCD). These OLED display devices utilize a pixel-defined layer (PDL) that demarcates and insulates the boundaries of each pixel. To form this PDL layer, a photosensitive acrylic compound is typically used. However, this material is unstable at high temperatures and has a relatively high dielectric constant, leading to a demand for alternative compounds.

[0006] Polysilsesquioxane compounds are copolymers of polysiloxane and have the characteristics of high heat resistance, high transparency, and low dielectric constant, 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 advantages of polysilsesquioxane binders, their application to negative-type photosensitive resin compositions is currently difficult.

[0007] Accordingly, the present invention sought to provide a photosensitive resin composition having excellent storage stability, surface coating properties, and resolution by using a polysilsesquioxane binder having appropriate developability for an alkaline aqueous solution.

[0008] According to one aspect of the present invention, a composition comprising a binder, a pigment, 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 photosensitive resin composition characterized in that an acid functional group is introduced into the binder and thus has an acid value.

[0011] Preferably, the photosensitive resin composition can be provided in which the binder has a carboxyl group introduced by a succinic acid compound.

[0012] Preferably, the photosensitive resin composition can be provided in which the succinic acid compound is an anhydrous succinic acid compound.

[0013] Preferably, with respect to the total weight of the photosensitive resin composition,

[0014] The binder is 18 to 50 wt%;

[0015] The pigment is present in an amount of 1 to 20 wt%;

[0016] The above multifunctional monomer is 0.1 to 10 wt%;

[0017] The photoinitiator is 0.1 to 5 wt%; and

[0018] The photosensitive resin composition can be provided, which comprises 30 to 80 wt% of the solvent.

[0019] Preferably, the photosensitive resin composition can be provided in which the succinic acid compound is triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride or trimethoxysilylbutyl succinic anhydride.

[0020] Preferably, a photosensitive resin composition can be provided in which the acid value of the binder is 5 to 38 mgKOH / g.

[0021] Preferably, a photosensitive resin composition can be provided in which the alkaline dissolution rate of the binder is 300 to 1000 Å / sec.

[0022] Preferably, a photosensitive resin composition can be provided in which no residue exists in a pattern cured film formed from the photosensitive resin composition.

[0023] Preferably, a photosensitive resin composition can be provided in which the minimum size confirmed in a pattern cured film formed from the photosensitive resin composition is less than 10 μm.

[0024] Preferably, for a pattern cured film formed from a photosensitive resin composition manufactured after storing the binder at room temperature (23°C) for 30 days,

[0025] There is no residue in the above pattern curing film,

[0026] A photosensitive resin composition can be provided in which the minimum size confirmed in the above pattern cured film is less than 10 μm.

[0027] Preferably, the photosensitive resin composition can provide a photosensitive resin composition that is used to form a PDL (pixel defined layer) layer included in an OLED display device.

[0028] According to another aspect of the present invention, a cured product manufactured by curing the photosensitive resin composition can be provided.

[0029] According to another aspect of the present invention, the photosensitive resin composition is applied,

[0030] A method for forming a pattern can be provided, which includes selectively exposing an applied photosensitive resin composition to light and then developing it.

[0031] According to the present invention, a photosensitive resin composition including a polysilsesquioxane-based binder having developability for an alkaline aqueous solution can be provided by controlling acid functional groups and double bonds within a polysilsesquioxane structure.

[0032] In addition, a photosensitive resin composition having excellent storage stability and good surface coating properties can be provided.

[0033] Additionally, a photosensitive resin composition that can be used to form a PDL (pixel defined layer) layer included in an OLED display device can be provided.

[0034] Hereinafter, the present invention will be described.

[0035] 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.

[0036] 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.

[0037]

[0038] As one embodiment of the present invention, the photosensitive resin composition may include a binder, a pigment, a multifunctional monomer, and a photoinitiator.

[0039] The binder may include a polysilsesquioxane-based binder. The polysilsesquioxane-based binder is a polysilsesquioxane compound, which may be prepared by polymerizing a silane-based monomer and a compound containing an acid functional group; or by polymerizing a silane-based monomer, a compound containing an acid functional group, and a compound containing a double bond. For example, the polysilsesquioxane-based binder may be 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, a compound containing an acid functional group, and a compound containing a double bond. At this time, RSiO is preferable. 3 / 2 Two or more silane compounds capable of forming a unit, RSiO 4 / 2 It can be manufactured by including at least one silane compound capable of forming a unit, a compound containing an acid functional group, and a compound containing a double bond. The silane monomer may include an alkoxy group, an oxime group, an acetoxy group, an epoxy group, a vinyl group, a cycloaliphatic group, etc., but is not limited thereto as long as it can form a 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 a cycloalkenyl group; an aryl group such as phenyl or xylyl; an aralkyl group such as benzyl; or a halogenated alkyl group.

[0040] RSiO 3 / 2Examples 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.

[0041] RSiO 4 / 2 Examples of silane compounds capable of forming units include, but are not limited to, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrapentoxysilane.

[0042] 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.

[0043] 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.

[0044] 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 the mole fraction of the compound containing one double bond in the molecule among the total monomers used for polymerizing the 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.

[0045]

[0046] The polysilsesquioxane binder may further include an acid functional group by polymerizing a compound including an acid functional group, and 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.

[0047] When polymerizing a polysilsesquioxane binder from a carboxylic acid compound, a sulfinyl compound, or a sulfonyl compound, the polysilsesquioxane binder may contain both an acid functional group and a double bond.

[0048] A polysilsesquioxane binder can reproducibly control the development speed of a resin composition by introducing an acid functional group and a double bond into the structure of the binder, and can have developability for an alkaline aqueous solution. Specifically, the acid functional group includes a carboxyl group, a sulfinic acid group, a sulfonic acid group, etc., and a carboxyl group can be preferably introduced, and since the acid functional group includes a double bond, a double bond can also be introduced into the polysilsesquioxane binder. In order to introduce an acid functional group into the structure of the polysilsesquioxane binder, a succinic acid compound, specifically 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 an acid functional group, the acid value of the polysilsesquioxane binder may be about 5 to 38 mgKOH / g, preferably about 10 to 35 mgKOH / g, and more preferably about 10 to 33 mgKOH / g.

[0049] A polysilsesquioxane binder can be prepared, for example, by mixing two or more silane monomers and a compound containing an acid functional group, reacting the mixture with an aqueous hydrochloric acid solution, and 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 stirring the reaction solution. Thereafter, the mixture is washed and purified to obtain a polysilsesquioxane binder. The silane monomer is RSiO. 3 / 2Silane compounds capable of forming units and RSiO 4 / 2 Silane compounds that can form units can be used, RSiO 3 / 2 Silane compounds capable of forming units and RSiO 4 / 2 The molar ratio of the silane compounds capable of forming the unit may be 1:1 to 5:1, preferably 1.5:1 to 3:1, and more preferably 2:1 to 3:1.

[0050]

[0051] 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 acid functional groups per molecule included in the compound containing an acid functional group may vary, but the mole fraction of the compound containing one acid functional group in the molecule among the total monomers used for polymerizing the polysilsesquioxane-based binder may be about 0.01 to 0.5, preferably about 0.02 to 0.4, and more preferably 0.06 to 0.4. For example, when a succinic anhydride compound is used, the mole fraction of the succinic anhydride compound (a compound containing an acid functional group) among the total monomers used for polymerizing the polysilsesquioxane-based binder may be about 0.01 to 0.20, and preferably about 0.03 to 0.20.

[0052] The polysilsesquioxane binder may be included in an amount of about 18 to 50 wt%, preferably about 18 to 40 wt%, and more preferably about 18 to 35 wt%, based on the total weight of the photosensitive resin composition.

[0053] The pigment may be one or more types of inorganic pigments or organic pigments. For example, black pigments, red pigments, blue pigments, green pigments, yellow pigments, etc. may be used, but are not particularly limited thereto. Specifically, a pigment selected from the group consisting of black pigments, red pigments, blue pigments, green pigments, yellow pigments, etc. may be used alone, or two or more types of pigments may be mixed and used, and the types of pigments are not particularly limited to these examples.

[0054] The pigment may be included in an amount of about 1 to 20 wt%, preferably about 5 to 15 wt%, based on the total weight of the photosensitive resin composition. When the above range is satisfied, the transmittance to light in the ultraviolet region is high when exposed to ultraviolet rays, so that sufficient curing can occur. If the pigment is included in an excessive amount, the light-blocking effect is reduced, and if it is included in an excessive amount, the transmittance to light in the ultraviolet region is significantly reduced, which may result in non-curing.

[0055] Examples of black pigments that can be used include, but are not limited to, aniline black, titanium black, carbon black, lactam black, and perylene 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]

[0058] The polyfunctional monomer may be a polyfunctional monomer having four or more functional groups to increase the reactivity to ultraviolet rays. For example, at least one selected from the group consisting of dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol ethoxylated tetraacrylate, and hexanediol diacrylate may be used. When the polyfunctional monomer is included in an amount of about 0.1 to 10 wt%, preferably about 1 to 5 wt%, based on the total weight of the photosensitive resin composition, sufficient curing upon exposure to ultraviolet rays can be achieved, thereby obtaining pattern visibility (high resolution), high heat resistance, and excellent reliability. If the polyfunctional monomer is included in an amount that is too small, the resolution may be reduced or the film residue rate may be reduced due to non-curing upon exposure to ultraviolet rays. If the polyfunctional monomer is included in an excessive amount, excessive curing may occur, resulting in poor resolution of the photosensitive resin composition and the generation of residue.

[0059] Photoinitiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (Irgacure OXE-01), 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, triethanolamine, Irgacure OXE-02, Irgacure OXE-03, TPO, TPO-L, etc. When the photoinitiator is included in an amount of about 0.1 to 5 wt%, preferably about 0.5 to 3 wt%, based on the total weight of the photosensitive resin composition, sufficient curing upon exposure to ultraviolet rays can be achieved, thereby obtaining pattern visibility (high resolution), high heat resistance, and excellent reliability. If the photoinitiator is included in an excessive amount, resolution may be reduced or the film residue rate may be reduced due to non-curing upon exposure to ultraviolet rays. If the photoinitiator is included in an excessive amount, unreacted initiators may adversely affect the physical properties of the photosensitive resin composition.

[0060] 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, At least one selected from the group consisting of dimethylacetamide, dimethylformamide, anisole, tetrahydrofuran, toluene, methanol, ethanol, and mixtures thereof may be used. When the solvent is included in an amount of about 30 to 80 wt% based on the total weight of the photosensitive resin composition, the photosensitive resin composition can have excellent viscosity for processability.

[0061]

[0062] As one embodiment of the present invention, a cured product can be manufactured by curing the photosensitive resin composition. For example, when lactam black is used as a black pigment, curing of the photosensitive resin composition can be achieved by irradiating it with ultraviolet rays in the range of 350 to 400 nm, which is a region 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.

[0063] As one embodiment of the present invention, a method for forming a pattern may include applying the photosensitive resin composition, selectively exposing the applied photosensitive resin composition to light, and then developing the photosensitive resin composition. Specifically, selectively exposing the photosensitive resin composition to light may be performed by using a photomask having a desired pattern formed thereon to distinguish between exposed and unexposed areas.

[0064] Hereinafter, the present invention is specifically described with reference to examples and comparative examples of the present invention.

[0065]

[0066] Synthesis Example 1. Synthesis of polysilsesquioxane binder

[0067] A 500 ml three-necked round-bottomed flask was charged with a molar ratio of 17:30:30:20:3 of methyltrimethoxysilane:phenyltrimethoxysilane:tetraethoxysilane:methacryloxypropyltrimethoxysilane:triethoxysilylpropyl succinic anhydride, 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 the polysilsesquioxane binder. After washing and purifying with deionized water and ethyl acetate, unreacted substances and impurities were removed by distillation under reduced pressure. Afterwards, PGMEA was added to obtain a polysilsesquioxane binder with a solid content of 50% (weight average molecular weight of approximately 5,000 to 7,000 g / mol).

[0068]

[0069] Synthesis Examples 2 to 5. Synthesis of polysilsesquioxane binders

[0070] Polysilsesquioxane binders of Synthetic Examples 2 to 5 were obtained in the same manner as in Synthetic Example 1, except that the molar ratio of mixing methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride was changed. The molar ratios of methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methacryloxypropyltrimethoxysilane, and triethoxysilylpropyl succinic anhydride used in each are shown in Table 1.

[0071]

[0072] Synthesis Example 6. Synthesis of a polysilsesquioxane binder

[0073] It was manufactured in the same manner as in Synthesis Example 2, but instead of the hydrochloric acid aqueous solution, 200 g of a potassium carbonate aqueous solution dissolved in 5% deionized water as a base catalyst was used as a catalyst.

[0074]

[0075] Synthesis Example Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Methyltrimethoxysilane 17 15 100 20 15 Phenyltrimethoxysilane 30 30 30 30 30 30 Tetraethoxysilane 30 30 30 30 30 30 Methacryloxypropyltrimethoxysilane 20 20 20 20 20 Triethoxysilylpropyl succinic anhydride 35 10 20 05 Synthesis Example Characteristics Catalyst Acid Acid Base Acid Value (mgKOH / g) 12.93 116.115 31.748 38.56 400 ADR (Å / sec) 36 25 117 56 10 333 129

[0076]

[0077] The acid value and ADR (Alkaline dissolution rate) of the polysilsesquioxane binders manufactured by Synthesis Examples 1 to 6 were confirmed.

[0078] In the case of Synthesis Example 6, triethoxysilylpropyl succinic anhydride was added, but the acid value was not measured because the carboxyl group was not introduced into the copolymer by reacting with the base catalyst.

[0079] ADR is the alkaline dissolution rate, and a higher ADR value indicates a faster pattern development speed. If the photosensitive resin composition is overdeveloped or underdeveloped, resolution may be reduced or the residual film rate may be poor, so it is preferable to have an ADR value in the range of 300 Å / sec to 1000 Å / sec.

[0080]

[0081] Example 1. Preparation of photosensitive resin composition

[0082] 17 wt% of the polysilsesquioxane binder of Synthesis Example 1, 9 wt% of lactam black as a pigment, 3 wt% of dipentaerythritol hexaacrylate as a polyfunctional monomer, 1 wt% of a photoinitiator (Irgacure OXE-02), and 70 wt% of PGMEA as a solvent were introduced into a reactor and stirred at room temperature to prepare a resin composition of Example 1.

[0083]

[0084] Examples 2 to 3 and Comparative Examples 1 to 3. Preparation of photosensitive resin composition

[0085] The resin compositions of Examples 2 to 3 and Comparative Examples 1 to 3 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.

[0086]

[0087] Experimental Example 1. Evaluation of Residue of Photosensitive Resin Composition

[0088] Each of the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 was spin-coated on an ITO substrate, and then soft-baked using a hot plate at about 110°C for about 70 seconds. Using a predetermined pattern mask, the intensity was 50 mW / cm at 365 nm. 2 After irradiating with ultraviolet rays, it was developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23±1℃ for about 70 seconds, and washed with ultrapure water. After that, hard baking was performed in an oven at about 230℃ for about 30 minutes to form a patterned cured film with a thickness of 1 μm. An optical microscope was used to check whether residue was found in the patterned cured film. A residue is an undeveloped portion remaining on a surface that was not irradiated with ultraviolet rays, and this was confirmed with an optical microscope. And it was evaluated according to the following criteria, which are shown in Table 2.

[0089] - No residue ◎: No residue when observed under an optical microscope

[0090] - Residue Normal △: When observed under an optical microscope, a small number of residues (5 or fewer) are present.

[0091] - No residue X: When observed under an optical microscope, multiple residues (more than 5) are present.

[0092]

[0093] Experimental Example 2. Resolution Evaluation of Photosensitive Resin Compositions

[0094] A pattern curing film was formed using the same method as in Experimental Example 1.

[0095] Using FE-SEM, the resolution of each specimen was evaluated based on the following criteria, and is shown in Table 2.

[0096] - ◎ (Good): Minimum pattern size is less than 5μm

[0097] - △ (Normal): The minimum size of the pattern is 5 μm or more and less than 10 μm.

[0098] - X (bad): The minimum size of the pattern is 10 μm or more.

[0099]

[0100] Experimental Example 3. Evaluation of Storage Stability of Photosensitive Resin Compositions

[0101] After storing the polysilsesquioxane copolymers of Synthetic Examples 1 to 3 at room temperature (23°C) for 30 days, resin compositions containing each of them were prepared in the same manner as in Example 1, and these were designated as Examples 4 to 6.

[0102] For Examples 4 to 6, the residue and resolution were confirmed in the same manner as in Experimental Examples 1 and 2.

[0103] Examples 4 to 6 were evaluated according to the following criteria, and the results are shown in Table 2.

[0104] For Comparative Examples 1 to 3, storage stability evaluation was not conducted because the residue and resolution evaluation results confirmed in Experimental Examples 1 and 2 were not good.

[0105] - ◎ (Good): No residue occurs, and the resolution (minimum pattern size) is less than 5 μm.

[0106] - X (bad): Residue occurs and the resolution (minimum size of the pattern) is 5 μm or more.

[0107]

[0108] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Residue ◎◎◎△×× Resolution ◎◎◎△△△ Storage stability ◎ (Example 4) ◎ (Example 5) ◎ (Example 6) ---

[0109]

[0110] When the results of Experimental Examples 1 to 3 are summarized, it was confirmed that the resin compositions of Examples 1 to 3 have excellent characteristics in terms of residue generation and resolution, and in particular, no residue is generated even after 30 days of storage at room temperature (23°C), and the resolution is excellent, so that they have superior performance in terms of storage stability.

[0111]

[0112] 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, pigment, multifunctional monomer, photoinitiator and solvent, The above binder comprises a polysilsesquioxane binder, A photosensitive resin composition, characterized in that the polysilsesquioxane binder has an acid value due to the introduction of an acid functional group into the binder.

2. In claim 1, A photosensitive resin composition in which the above binder has a carboxyl group introduced by a succinic acid compound.

3. In claim 2, A photosensitive resin composition wherein the above succinic acid compound is an anhydrous succinic acid compound.

4. In claim 1, With respect to the total weight of the photosensitive resin composition, The binder is 18 to 50 wt%; The pigment is present in an amount of 1 to 20 wt%; The above polyfunctional monomer is 0.1 to 10 wt%; The photoinitiator is 0.1 to 5 wt%; and A photosensitive resin composition comprising 30 to 80 wt% of the solvent.

5. In claim 2, A photosensitive resin composition, wherein the above succinic acid compound is triethoxysilylpropyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilylbutyl succinic anhydride or trimethoxysilylbutyl succinic anhydride.

6. In claim 1, A photosensitive resin composition, wherein the acid value of the binder is 5 to 38 mgKOH / g.

7. In claim 1, A photosensitive resin composition, wherein the alkali dissolution rate of the binder is 300 to 1000 Å / sec.

8. In claim 1, A photosensitive resin composition in which no residue exists in a pattern cured film formed from the photosensitive resin composition.

9. In claim 1, A photosensitive resin composition, wherein the minimum size confirmed in a pattern cured film formed from the photosensitive resin composition is less than 10 μm.

10. In claim 1, Regarding the pattern cured film formed from the photosensitive resin composition manufactured after storing the above binder at 23°C for 30 days, There is no residue in the above pattern curing film, A photosensitive resin composition, wherein the minimum size confirmed in the above pattern cured film is less than 10 μm.

11. In claim 1, The photosensitive resin composition is a photosensitive resin composition used to form a PDL (pixel defined layer) layer included in an OLED display device.

12. A cured product manufactured by curing the photosensitive resin composition of any one of claims 1 to 11.

13. Applying the photosensitive resin composition of any one of claims 1 to 11, A method for forming a pattern, comprising selectively exposing a coated photosensitive resin composition to light and then developing it.