Photosensitive resin composition, pattern and display device using the same

Abstract

The present invention relates to a photosensitive resin composition comprising (A) a photoinitiator, (B) a thiol compound containing an ether bond, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a solvent, wherein the thiol compound containing an ether bond (B) comprises one or more compounds selected from those represented by Formula 1 and Formula 2, and the photopolymerizable compound (D) comprises a urethane acrylate oligomer, thereby having no residue, excellent physical and environmental reliability, and excellent storage stability, as well as a pattern formed therefrom and a display device.

Description

Technology Field

[0001] The present invention relates to a photosensitive resin composition, a pattern formed therefrom, and a display device. Background Technology

[0002] In the display field, photosensitive resin compositions are used to form various cured patterns, such as photoresists, insulating films, protective films, black matrices, and column spacers. Specifically, photosensitive resin compositions are selectively exposed and developed by a photolithography process to form desired patterns; in this process, high-sensitivity photosensitive resin compositions are required to improve process yield and enhance the physical properties of the application target.

[0003] Specifically, the pattern formation of the photosensitive resin composition is based on photolithography, that is, the change in polarity and crosslinking reaction of the polymer caused by a photoreaction. In particular, the pattern formation utilizes the characteristic of the change in solubility in a solvent, such as an alkaline aqueous solution, after exposure.

[0004] A photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocured pattern. In order to improve process yield and enhance the physical properties of the application target during this process, a photosensitive resin composition having excellent chemical and physical properties is required.

[0005] In addition, the curing conditions of photosensitive resin compositions have conventionally been carried out at temperatures of 220°C or higher, but there is a growing need for low-temperature curing to prevent deformation on the substrate that occurs at high temperatures. However, when the post-bake temperature is lowered for low-temperature curing, there are problems such as reduced reactivity and decreased reliability of the formed pattern.

[0006] In addition, when curing at low temperature, not only is the heat resistance of the photosensitive resin composition reduced, but there are also difficulties such as reduced chemical resistance properties like swelling due to surface penetration and reduced adhesion, reduced adhesion to the underlying substrate, and the occurrence of scratches due to exposure to solvents used in subsequent processes.

[0007] Korean Patent Publication No. 10-2009-0094556 discloses a photosensitive resin composition capable of low-temperature curing, comprising: (A) as a binder resin, (i) epoxy resin and (ii) one or more alkali-soluble resins selected from acrylate resin, photopolymer resin and mixtures thereof; (B) epoxy curing agent; (C) crosslinkable monomer having an ethylene-based double bond; (D) pigment; (E) photopolymerization initiator; and (F) solvent.

[0008] However, although the above-mentioned photosensitive resin composition enables low-temperature curing, it still suffers from poor resolution in pattern formation and is not generally reliable after formation, making it difficult to use industrially; therefore, a solution to this problem is required. Prior art literature

[0009] Republic of Korea Published Patent Application No. 10-2009-0094556 The problem to be solved

[0010] The present invention aims to improve upon the problems of the aforementioned prior art and to provide a photosensitive resin composition with excellent environmental reliability, such as heat resistance, alkali resistance, and chemical resistance, under low-temperature curing conditions.

[0011] In addition, the present invention aims to provide a photosensitive resin composition having excellent physical reliability, such as excellent adhesion and no scratching.

[0012] In addition, the present invention aims to provide a photosensitive resin composition that does not generate residue, enables the achievement of high resolution with excellent process margins in pattern formation, and exhibits excellent preservation stability in processes after pattern formation.

[0013] In addition, the present invention aims to provide a pattern and display device of excellent quality by being manufactured using the above-described photosensitive resin composition.

[0014] However, the problems that this invention seeks to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below. means of solving the problem

[0015] The present invention provides a photosensitive resin composition comprising (A) a photoinitiator, (B) a thiol compound containing an ether bond, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a solvent, wherein the (B) thiol compound containing an ether bond comprises one or more compounds selected from the compounds represented by the following chemical formulas 1 and 2, and the (D) photopolymerizable compound comprises a urethane acrylate oligomer.

[0016] [Chemical Formula 1]

[0017]

[0018] (In the above Chemical Formula 1, R1 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R2 to R4 are each independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with hydrogen or one or more thiol groups.)

[0019] [Chemical Formula 2]

[0020]

[0021] (In the above Chemical Formula 2, R5 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R6 to R 10 Each is independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, substituted with hydrogen or one or more thiol groups.

[0022] In addition, the present invention provides a pattern comprising the above-mentioned photosensitive resin composition.

[0023] In addition, the present invention provides a display device including the above pattern. Effects of the invention

[0024] The photosensitive resin composition of the present invention includes a combination of a specific thiol compound and urethane acrylate, providing the effect of enabling the realization of high-resolution patterns with excellent physical and environmental reliability, no residue during pattern formation, and excellent process margins.

[0025] In addition, it provides excellent storage stability even under high temperature conditions, so that shrinkage does not occur. Specific details for implementing the invention

[0026] The present invention will be described in more detail below.

[0027] The present invention relates to a photosensitive resin composition, a pattern, and a display device comprising a thiol compound containing ether bonds of a specific structure and a urethane acrylate oligomer, which enables low-temperature curing, allows for the achievement of high resolution without residue even under low-temperature curing conditions, and has excellent characteristics in many aspects regarding the reliability of the cured pattern.

[0028] In addition, in one embodiment of the present invention, by including one or more thiol compounds selected from compounds represented by Formula 1 and Formula 2 and a urethane acrylate oligomer together, the characteristic of improved storage stability under high temperature conditions can be achieved.

[0029] In the present invention, the low-temperature curing temperature can be based on the post-baking temperature.

[0030] The “low temperature” of the present invention may be a temperature of 150°C or lower, preferably 120°C or lower, more preferably 100°C or lower.

[0032] Embodiments of the present invention will be described in more detail below. However, the terms used in this specification are for describing embodiments and are not intended to limit the present invention. In this specification, the singular form includes the plural form unless specifically stated otherwise.

[0033] As used herein, “comprises” and / or “comprising” are used to mean that one or more other components, steps, and / or components other than the mentioned components, steps, and / or components are not excluded.

[0035] Photosensitive resin composition

[0036] The photosensitive resin composition of the present invention comprises (A) a photoinitiator, (B) a thiol compound containing an ether bond, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a solvent, and

[0037] The thiol compound containing the above (B) ether bond comprises one or more selected from the compounds represented by the following chemical formulas 1 and 2, and

[0038] The above (D) photopolymerizable compound is characterized by comprising a urethane acrylate oligomer.

[0039] [Chemical Formula 1]

[0040]

[0041] (In the above Chemical Formula 1, R1 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R2 to R4 are each independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with hydrogen or one or more thiol groups.)

[0042] [Chemical Formula 2]

[0043]

[0044] (In the above Chemical Formula 2, R5 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R6 to R 10 Each is independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, substituted with hydrogen or one or more thiol groups.

[0045] When including a thiol compound containing one or more ether bonds selected from the compounds represented by (B) Chemical Formula 1 and Chemical Formula 2 and a urethane acrylate oligomer, no residue is generated, heat resistance, alkali resistance and chemical resistance are good, adhesion is excellent, no scratches occur, and storage stability is excellent.

[0046] Specifically, when including a thiol compound containing one or more ether bonds selected from the compounds represented by (B) Chemical Formula 1 and Chemical Formula 2 and a urethane acrylate oligomer, it acts to improve adhesion to the underlying substrate, thereby providing resistance to adhesion and scratches, and can have an advantage in terms of improved chemical resistance compared to when used alone.

[0047] The photosensitive resin composition of the present invention is described in detail below according to its constituent components.

[0049] (A) Photoinitiator

[0050] The above photoinitiator plays a role in initiating a radical reaction of a photosensitive resin composition to cause curing and improve sensitivity. It is not specifically limited in the present invention, and any compound that generates radicals capable of initiating the polymerization of the photopolymerizable compound described below upon exposure to radiation such as visible light, ultraviolet light, far-ultraviolet light, electron beams, or X-rays may be used without limitation. Representative examples of the above photoinitiator include acetophenone-based compounds, benzophenone-based compounds, nonimidazole-based compounds, triazine-based compounds, oxime ester-based compounds, and thioxanthone-based compounds. In the present invention, the photoinitiator may be used alone or in a mixture of two or more types, and it is preferable to use one or more oxime ester-based compounds.

[0051] Examples of the above acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

[0052] Examples of the above benzophenone compounds include benzophenone, 2,2'-hydroxy-4,4'-dimethoxybenzophenone, o-methyl benzoylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0053] The above non-imidazole compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, Examples include 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

[0054] The above triazine compounds include, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, Examples include 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0055] Examples of the above oxime ester compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione-1-(4-phenylthio)phenyl-2-(o-benzoyloxime), ethanone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(o-acetyloxime), and commercially available products include CGI-124 (Ciba-Geigy), CGI-224 (Ciba-Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeka), and NCI-831 (Adeka).

[0056] Examples of the above thioxantone-based compounds include 2-isopropylthioxantone, 4-isopropylthioxantone, 2,4-diethylthioxantone, 2,4-dichlorothioxantone, 1-chloro-4-propoxythioxantone, etc.

[0057] Other examples include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and commercially available products include Irgacure 819 (BASF).

[0058] The above photoinitiator may be used in combination with a photopolymerization initiation aid. The above photopolymerization initiation aid may be used to promote the polymerization of a photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator.

[0059] Examples of the above photopolymerization initiation aids include amine compounds and alkoxyanthracene compounds. Specific examples of the above amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as mihilersketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, etc., among which 4,4'-di(N,N'-dimethylamino)-benzophenone is preferred.

[0060] Specific examples of the above alkoxianthracene compounds include 9,10-dimethoxycyanthracene, 2-ethyl-9,10-dimethoxycyanthracene, 9,10-diethoxycyanthracene, and 2-ethyl-9,10-diethoxycyanthracene. The above photopolymerization initiation aids may each be used individually or in combination of two or more types. Additionally, the above photopolymerization initiation aid may be a commercially available product such as EAB-F (manufactured by Hodogaya Kagaku Kogyo Co., Ltd.).

[0061] Specific examples of a preferred combination of the above photoinitiator and photopolymerization initiation aid include diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; and 1-hydroxycyclohexylphenylketone and 4,4'-bis(diethylamino)benzophenone. Examples include an oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; a combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone, and preferably a combination of 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone, a combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-di(N,N'-dimethylamino)-benzophenone.

[0062] When the above photoinitiator and the photopolymerization initiation aid are used together, it is preferable that the content of the photopolymerization initiation aid be 0.01 to 5 moles per 1 mole of the photopolymerization initiator. It is desirable that the photopolymerization initiation aid be included within the above content range because it increases the sensitivity of the photosensitive resin composition and improves the productivity of the cured film formed using this composition.

[0063] The above photoinitiator may be included in an amount of 0.05 to 20 weight%, preferably 0.5 to 10 weight%, based on the total weight of the photosensitive resin composition. When included within this range, the photosensitive resin composition becomes highly sensitive, which is desirable in terms of shortening exposure time, facilitating pattern formation control, and improving curability and straightness. When included in an amount exceeding 20 weight%, the line width is excessively enlarged, making it impossible to maintain high resolution.

[0065] (B) Thiol compounds containing ether bonds

[0066] The present invention comprises a thiol (-SH) compound containing an ether (-O-) bond, wherein the thiol compound containing the ether bond comprises one or more compounds selected from those represented by the following chemical formulas 1 and 2.

[0067] [Chemical Formula 1]

[0068]

[0069] [Chemical Formula 2]

[0070]

[0071] In the above chemical formula 1, R1 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R2 to R4 may each independently be a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with hydrogen or one or more thiol groups.

[0072] In the above Chemical Formula 2, R5 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R6 to R 10 Each may independently be a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, substituted with hydrogen or one or more thiol groups.

[0073] More specifically, the thiol compound containing the ether bond may be represented by the following chemical formula 4 or chemical formula 5.

[0074] [Chemical Formula 4]

[0075]

[0076] In the above chemical formula 4, R 13 is an alkylene group having 1 to 10 carbon atoms, and m1 and n1 are each independently integers from 1 to 3, and m1 + n1 = 4.

[0077] [Chemical Formula 5]

[0078]

[0079] In the above chemical formula 5, R 14 Each is independently an alkylene group having 1 to 10 carbon atoms, and m2, m3, n2 and n3 are each independently integers from 1 to 3, m2+n2=3, and m3+n3=3.

[0080] In the past, compounds used as thiol compounds, such as pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptobutyrate), all contain ester bonds within their molecular structures. Thiol compounds containing such ester bonds exhibit high reactivity to solvent decomposition, which significantly reduces water resistance and alkali resistance, and may also exhibit inferior properties such as long-term storage stability and stability over time. However, the photosensitive resin composition containing a thiol compound containing ether bonds according to the present invention can possess excellent properties of heat resistance, alkali resistance, and chemical resistance due to its high solvent decomposition resistance. In addition, the photosensitive resin composition of the present invention can exhibit excellent adhesion to a substrate due to the flexible framework of a thiol compound containing ether bonds, and exhibits a ratio of development speed such that the exposed and unexposed areas are clearly distinct due to the excellent contrast ratio even in low-temperature processes, and can have excellent storage stability characteristics such as no surface damage, swelling, or film shrinkage occurs even when exposed to a stripping solution in a subsequent process.

[0081] The thiol compound containing ether bonds according to the present invention may be included in an amount of 0.01 to 25 weight%, preferably 0.01 to 15 weight%, and more preferably 0.05 to 10 weight% based on the total weight of the photosensitive resin composition. If included in an amount less than the above, problems such as swelling and film shrinkage may occur when exposed to a stripping solution in a subsequent process, and if included in an amount exceeding the above, problems such as residue may occur and resolution may be reduced because the unexposed portion is not dissolved in the developer solution.

[0083] (C) Alkali-soluble resin

[0084] The above alkali-soluble resin (C) is a component that imparts solubility to the alkaline developer used in the development process, and can be used without limitation as long as it is soluble in the alkaline developer. A common method is to impart an acid value by introducing carboxyl groups into the resin to enable solubility in the alkaline developer. It can be manufactured by copolymerizing an ethylenically unsaturated monomer (c1) having carboxyl groups, or by imparting an acid value by reacting an acid anhydride with a resin copolymer (c2) having hydroxyl groups. In this case, the acid value of the alkali-soluble resin (C) is preferably 30 to 200 mgKOH / g. When the acid value of the alkali-soluble resin (C) is less than 30 mgKOH / g, it is difficult to secure a sufficient development speed for the colored photosensitive resin composition, and when it exceeds 200 mgKOH / g, the adhesion to the substrate is reduced, making it easy for a short circuit of the pattern to occur, and compatibility with the colorant is a problem, causing the colorant in the colored photosensitive resin composition to precipitate or the storage stability of the colored photosensitive resin composition to decrease, making it easy for the viscosity to increase.

[0085] Specific examples of the above ethylenically unsaturated monomer (c1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferred.

[0086] A method for imparting an acid value to a resin copolymer (c2) having the above-mentioned hydroxyl group by reacting an acid anhydride with a hydroxyacrylate copolymer is to impart an acid value by additionally reacting an acid anhydride with the hydroxyacrylate copolymer, but is not limited thereto.

[0087] The above hydroxyacrylates are typically as follows.

[0088] Hydroxyethyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and N-hydroxyethyl acrylamide; unsaturated monomers (c3) copolymerizable during the preparation of the alkali-soluble resin (C) are exemplified below but are not necessarily limited thereto.

[0089] Specific examples of copolymerizable unsaturated polymer monomers (c3) include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether; N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, etc.; Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate; cyclopentyl (meth)acrylates such as cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2-dicyclofentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate;

[0090] Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

[0091] There are unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane.

[0092] The monomers exemplified by the copolymerizable unsaturated monomers (c3) above can each be used alone or in combination of two or more types.

[0093] The alkali-soluble resin of the present invention may be included in an amount of 1 to 80 weight%, preferably 1 to 70 weight%, and more preferably 1 to 50 weight% based on the total weight of the photosensitive resin composition. When the above content range is satisfied, it is desirable because the solubility in the developer is sufficient to facilitate pattern formation, and the reduction of the film in the pixel portion of the exposed area is prevented during development, thereby improving the omission of non-pixel portions.

[0095] (D) Photopolymerizable compounds

[0096] The photopolymerizable compound in the photosensitive resin composition of the present invention must be a compound capable of polymerizing by the action of the photoinitiator (A) described above. The present invention is characterized by comprising a urethane acrylate oligomer.

[0097] Specifically, the urethane acrylate oligomer may be represented by the following chemical formula 3.

[0098] [Chemical Formula 3]

[0099]

[0100] In the above chemical formula 3, m is an integer from 1 to 10, X is an m+1 hydrocarbon group, and Y may be a straight-chain alkylene group having 6 to 13 carbon atoms, an alkylene group comprising a saturated hydrocarbon ring structure, or an alkylene group comprising an aromatic ring structure. R 11 and R12 They can be hydrogen or methyl groups independently of each other.

[0101] More specifically, the urethane acrylate oligomer represented by the above chemical formula 3 may comprise one or more compounds selected from the compounds represented by the following chemical formulas D-1 to D-3.

[0102] [Chemical Formula D-1]

[0103]

[0104] [Chemical Formula D-2]

[0105]

[0106] [Chemical Formula D-3]

[0107]

[0108] When the urethane acrylate oligomer according to the present invention is included, the adhesion to the lower substrate and scratch characteristics can be improved, and when included together with the thiol compound, it can have even better characteristics in terms of chemical resistance and reliability.

[0109] The above urethane acrylate oligomer has a weight average molecular weight of 500 to 20,000, preferably 500 to 10,000.

[0110] In addition to urethane acrylate oligomers, monofunctional monomers, difunctional monomers, or polyfunctional monomers may be used as photopolymerizable compounds, and the present invention is not particularly limited.

[0111] Specific examples of the above monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. Specific examples of the above difunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. Specific examples of the above-mentioned polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Among these, a polyfunctional monomer with two or more functions is preferably used.

[0112] In the photosensitive resin composition of the present invention, the content of the photopolymerizable compound may be 1 to 80 weight%, preferably 1 to 70 weight%, and more preferably 5 to 70 weight% based on the total weight of the photosensitive resin composition of the present invention. When the photopolymerizable compound is included within the above content range, it is desirable in terms of good strength or smoothness.

[0114] (E) Solvent

[0115] In the present invention, the solvent may be any solvent used in conventional photosensitive resin compositions without special limitation, as long as it is effective in dissolving other components included in the photosensitive resin composition according to the present invention, and ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amides are particularly preferred.

[0116] Specifically, the above solvent comprises ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; and aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene. Examples include ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl ethoxypropionate and methyl methoxypropionate; and cyclic esters such as γ-butyrolactone.

[0117] The above solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coating and drying properties, and more preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. may be used.

[0118] The above solvents can each be used individually or in a mixture of two or more types.

[0119] The above solvent may be included in a remainder amount such that the total weight of the photosensitive resin composition is 100% by weight. Specifically, in the present invention, "remainder" refers to the remainder amount such that the total weight of the composition, which includes the essential components of the present invention and other additional components, is 100% by weight, and the meaning of "remainder" does not limit the composition of the present invention to not including additional components. For example, it may be 10 to 90% by weight with respect to the total weight of the photosensitive resin composition of the present invention, and preferably 15 to 90% by weight. When the above solvent is included within the above range, it provides the effect of improving applicability when applied using an application device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes also called a die coater), or inkjet.

[0121] (F) Additives

[0122] In addition, the photosensitive resin composition according to the present invention may further include additives to enhance the coating properties, adhesion, etc. of the cured film, as required by a person skilled in the art, in addition to the aforementioned components, to a extent that does not impair the purpose of the present invention. To this end, it may further include components generally used in the relevant technical field, such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, UV absorbers, and / or anti-aggregation agents, and may additionally include additives commonly used in the technical field to which the present invention belongs. One of these may be used alone, or two or more may be used in combination and in any ratio.

[0123] Specific examples of the above other polymer compounds include curable resins such as epoxy resin and maleimide resin, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

[0124] The above-mentioned curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, etc.

[0125] Specific examples of epoxy compounds in the above curing agent include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, etc.

[0126] Specific examples of oxetane compounds in the above curing agent include carbonate bis-oxetane, xylene bis-oxetane, adipate bis-oxetane, terephthalate bis-oxetane, cyclohexanedicarboxylic acid bis-oxetane, etc.

[0127] The above-mentioned curing agent may be used in combination with a curing aid compound capable of causing ring-opening polymerization of the epoxy groups of the epoxy compound and the oxetane backbone of the oxetane compound. Examples of the above-mentioned curing aid compounds include polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, etc. The above-mentioned polycarboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the above-mentioned epoxy resin curing agents include the product name (Adeka Hadona EH-700) (manufactured by Adeka Industry Co., Ltd.), the product name (Ricasitdo HH) (manufactured by Shin Nippon Iwa Co., Ltd.), and the product name (MH-700) (manufactured by Shin Nippon Iwa Co., Ltd.). The curing agents exemplified above may be used alone or in a mixture of two or more types.

[0128] The above surfactant may be used to further improve the film-forming properties of the photosensitive resin composition, and may be included for the purpose of acting as a silane coupling agent or leveling agent to enhance coating properties and adhesion. Examples include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, etc., which may be used individually or in combination of two or more types. It is more preferable to use silicone-based and / or fluorine-based surfactants, but is not limited thereto.

[0129] Examples of the above silicone-based surfactants include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH-8400 from Dow Corning Toray Silicon, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 from GE Toshiba Silicon.

[0130] Examples of the above-mentioned fluorine-based surfactants include commercially available products such as Megapiece F-470, F-471, F-475, F-482, F-489, F-554 from Dai Nippon Ink Co., Ltd. Each of the surfactants exemplified above can be used individually or in combination of two or more types.

[0131] Specific examples of the above-mentioned adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. The adhesion promoters exemplified above can each be used individually or in combination of two or more types.

[0132] The above adhesion promoter may be included in a weight fraction of typically 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition.

[0133] Specific examples of the above antioxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, etc.

[0134] Specific examples of the above-mentioned ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiriazole, alkoxybenzophenone, etc.

[0135] Specific examples of the above anti-coagulant include sodium polyacrylate.

[0136] The above additive may be appropriately added and used by those skilled in the art within a range that does not impede the effects of the present invention. For example, the above additive may be used in an amount of 0.05 to 10 weight%, preferably 0.1 to 9 weight%, more preferably 0.1 to 8 weight% with respect to the total weight of the photosensitive resin composition, but is not limited thereto.

[0138] <Pattern made of photosensitive resin composition>

[0139] The present invention comprises a pattern prepared from a cured product of the photosensitive resin composition described above and said pattern.

[0140] The pattern according to the present invention may be characterized by being cured at 100°C or lower, and the pattern according to the present invention may be manufactured by a method known in the art, except that it is formed from the photosensitive resin composition described above. In the present invention, the standard for the curing temperature may be the pre-bake and / or post-bake temperature.

[0141] In forming a photocurable pattern, the pattern can be formed by coating the above-described photosensitive resin composition onto a substrate and then performing exposure and development steps. At this time, a pre-bake or post-bake process may be performed between each step. The heating temperature and heating time of the pre-bake are selected according to the solvent used, for example, at a temperature of 80°C to 100°C for 1 to 3 minutes. The exposure is performed by an exposure machine and sensitizes only the portion corresponding to the pattern by exposing through a photomask. The light irradiated at this time may be, for example, visible light, ultraviolet light, X-rays, and electron beams. At this time, the exposure time is not particularly limited and can be appropriately varied depending on the exposure device, the wavelength of the irradiated light, or the amount of exposure; however, the preferred exposure time can be varied within the range of 5 to 250 seconds. Subsequently, as a step to increase hardness by increasing the adhesion between the patterned film and the substrate, a hard bake may be performed by heat treating for 10 to 120 minutes at a curing temperature, preferably 80 to 100°C, to complete the curing. The heat treatment may be performed using an oven or a hot plate, but is not limited thereto.

[0142] The above pattern may be a photocuring pattern selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern including a scatterer, and a pattern including a quantum dot.

[0143] The photocuring pattern according to the present invention can form a coating film exhibiting an excellent residual film rate by using a thiol compound containing an ether structure to prevent radicals from being oxygen-impaired by oxygen during the photolithography process, and can prevent swelling, shrinkage, or reduced adhesion of the coating film by suppressing the decomposition of soluble agents when exposed to a stripping solution in a subsequent process, and has additional advantages in adhesion to the underlying substrate and scratch resistance by including a urethane acrylate oligomer.

[0144] In addition, the photocuring pattern according to the present invention has excellent process margin, so high resolution of C / H 5 µm or less can be achieved.

[0146] <Display device>

[0147] The present invention provides a display device comprising a pattern manufactured from the photosensitive resin composition described above. Specifically, the display device may include, but is not limited to, a liquid crystal display (LCD), an organic EL display (including OLED and QLED), a flexible display, a liquid crystal projector, a display device for a game console, a display device for a mobile terminal such as a mobile phone, a display device for a digital camera, a display device for a navigation system, etc. Except for having the pattern, the display device may further include configurations commonly used in the field.

[0149] Hereinafter, experimental examples including specific embodiments and comparative examples are presented to aid in understanding the present invention; however, these are merely illustrative of the present invention and are not intended to limit the appended claims. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the present invention, and it is also natural that such variations and modifications fall within the scope of the appended claims. Unless otherwise specified, "%" and "parts" in the examples refer to "mass%" and "mass parts," respectively.

[0151] Synthesis Example 1: Synthesis of Pentaerythritol Tripropanethiol (B-1)

[0152] 1.37 mol of pentaerythritol trialylether was added to a round-bottom flask and heated to 40°C. 4.51 mol of thioacetic acid was added dropwise to achieve a molar ratio of 1:3.3 with pentaerythritol trialylether, and the mixture was stirred at 40°C for 4 hours. 560 g of a 20% aqueous ammonia solution was added to the reaction mixture, and the reaction was carried out at 55°C for 15 hours. After separating the organic layer, 490 g of toluene and 350 g of a 5% aqueous sulfuric acid solution were added and washed; the organic layer was then separated and taken, and 350 g of water was added to the organic layer.

[0153] The organic layer was separated, concentrated, and dried to synthesize pentaerythritol tripropanethiol (478 g, yield 98%) represented by the following chemical formula A-1 (referred to as PEPT) as a colorless, transparent oil, and the results of NMR analysis are shown below.

[0154] [Chemical Formula A-1]

[0155]

[0156] <Pentaerythritol Tripropanethiol NMR Analysis Results>

[0157] 1H-NMR (400MHz, CDCl3): δ 1.35 (t,3H), δ 1.80-1.86 (m,6H), δ 2.55-2.61 (m, 6H), δ 2.79 (br, 1H), δ 3.40 (s, 6H), δ 3.48 (t, 6H), δ 3.65 (s, 2H)

[0159] Synthesis Example 2: Synthesis of dipentaerythritol tetrapropanethiol (B-2)

[0160] Dipentaerythritol tetrapropanethiol represented by the following chemical formula A-2 was synthesized in the same manner as in Synthesis Example 1 above, except that the pentaerythritol trialyl ether was replaced with dipentaerythritol tetraallyl ether and thioacetic acid was added dropwise at a molar ratio of 1:4.4.

[0161] [Chemical Formula A-2]

[0162]

[0164] Synthesis Example 3: Synthesis of dipentaerythritol pentapropanethiol (B-3)

[0165] Dipentaerythritol pentapropanethiol represented by the following chemical formula A-3 was synthesized in the same manner as in Synthesis Example 1 above, except that pentaerythritol trialylether was replaced with dipentaerythritol pentaallylether and thioacetic acid was added dropwise at a molar ratio of 1:5.5.

[0166] [Chemical Formula A-3]

[0167]

[0169] Synthesis Example 4: Synthesis of Photopolymerizable Compound D-1

[0170] Polyol and hexamethylene diisocyanate were added to a 4-neck flask equipped with a thermometer, and the temperature was raised to 80°C and reacted for 3 hours to synthesize a prepolymer. Polyethylene Glycol Monomethyl Ether Acrylate was added to the synthesized prepolymer and reacted again at 80°C until the residual isocyanate groups disappeared, at which point the reaction was terminated to synthesize a urethane acrylate oligomer. The synthesized photopolymerizable compound D-1 has 2 reactive groups and a weight-average molecular weight (Mw) of 10,000.

[0172] Synthesis Example 5: Synthesis of Photopolymerizable Compound D-2

[0173] Polyol and isophorene diisocyanate were added to a 4-neck flask equipped with a thermometer, and the temperature was raised to 80°C and reacted for 3 hours to synthesize a prepolymer. Pentaerythritol triacrylate was added to the synthesized prepolymer and reacted again at 80°C until the residual isocyanate groups disappeared, at which point the reaction was terminated to synthesize a urethane acrylate oligomer. The synthesized photopolymerizable compound D-2 has 6 reactive groups and a weight-average molecular weight (Mw) of 15,000.

[0175] Synthesis Example 6: Synthesis of Photopolymerizable Compound D-3

[0176] Polyol and Tolylene-2,4-diisocyanate were added to a 4-neck flask equipped with a thermometer, and the temperature was raised to 80°C and reacted for 3 hours to synthesize a prepolymer. Pentaerythritol triacrylate was added to the synthesized prepolymer and reacted again at 80°C until the residual isocyanate groups disappeared, at which point the reaction was terminated to synthesize a urethane acrylate oligomer. The synthesized photopolymerizable compound D-3 has 6 reactive groups and a weight-average molecular weight (Mw) of 18,000.

[0178] Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions

[0179] Photosensitive resin compositions according to the examples and comparative examples were prepared by referring to the composition and weights listed in Tables 1 and 2 below.

[0181] (Unit: weight%) Examples 1 2 3 4 5 6 7 8 9 10 11 12 Photoinitiator A 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 thiol compounds B-1 0.11 0.11 0.11 - - 0.11 0.11 0.11 0.11 0.01 0.15 0.21 B-2 - - - 0.11 - - - - - - - - B-3 - - - - 0.11 - - - - - - - B-4 - - - - - - - - - - - - B-5 - - - - - - - - - - - - B-6 - - - - - - - - - - - - Alkali-soluble resin C 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.34 1.26 1.23 photopolymerizable compounds D-1 0.86 - - 0.86 0.86 0.04 0.11 0.21 0.43 0.89 0.84 0.82 D-2 - 0.86 - - - - - - - - - - D-3 - - 0.86 - - - - - - - - - D-4 - - - - - - - - - - - - D-5 - - - - - - - - - - - - D-6 - - - - - - - - - - - - D-7 - - - - - 0.81 0.75 0.64 0.43 - - - solvent E 7.49 7.49 7.49 7.49 7.49 7.50 7.49 7.50 7.49 7.50 7.50 7.49 additives F 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Total 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0

[0183] (Unit: weight%) Comparative example 1 2 3 4 5 6 7 Photoinitiator A 0.21 0.21 0.21 0.21 0.21 0.21 0.21 thiol compounds B-1 0.11 0.11 0.11 - - - - B-2 - - - - - - - B-3 - - - - - - - B-4 - - - 0.11 - - 0.11 B-5 - - - - 0.11 - - B-6 - - - - - 0.11 - Alkali-soluble resin C 1.29 1.29 1.29 1.29 1.29 1.29 1.29 photopolymerizable compounds D-1 - - - 0.86 0.86 0.86 - D-2 - - - - - - - D-3 - - - - - - - D-4 0.86 - - - - - 0.86 D-5 - 0.86 - - - - - D-6 - - 0.86 - - - - D-7 - - - - - - - solvent E 7.49 7.49 7.49 7.49 7.49 7.49 7.49 additives F 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Total 10.0 10.0 10.0 10.0 10.0 10.0 10.0

[0184] - (A) Photoinitiator: Irgacure OXE-01 (manufactured by BASF)

[0185] - (B-1) Thiol compound: Thiol compound according to Synthesis Example 1

[0186] - (B-2) Thiol compound: Thiol compound according to Synthesis Example 2

[0187] - (B-3) Thiol compound: Thiol compound according to Synthesis Example 3

[0188] - (B-4) Thiol compound: Trimethylolpropane dipropanethiol (TMPT, manufactured by SC Organic Chemical)

[0189] - (B-5) Thiol compound: 1,4-bis(3-mercaptobutylyloxy)butane (manufactured by Showa Denko)

[0190] - (B-6) Thiol compound: Dipentaerythritol hexakis(3-mercaptopropionate, manufactured by SC Organic Chemical)

[0191] - (C) Alkali-soluble resin: SPCY-1L (Acrylic resin, manufactured by Showa Denko)

[0192] - (D-1) Photopolymerizable compound: Photopolymerizable compound according to Synthesis Example 4

[0193] - (D-2) Photopolymerizable compound: Photopolymerizable compound according to Synthesis Example 5

[0194] - (D-3) Photopolymerizable compound: Photopolymerizable compound according to Synthesis Example 6

[0195] - (D-4) Photopolymerizable Compound: Miramer® (Miwon Trading Co.)

[0196] - (D-5) Photopolymerizable Compound: Miramer® (Miwon Trading Co.)

[0197] - (D-6) Photopolymerizable compound: MIRAMER SC9060 (Miwon Trading Co.)

[0198] - (D-7) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Explosives)

[0199] - (E) Solvent: Propylene glycol monomethyl ether acetate (Manufactured by Sigma-Aldrich)

[0200] - (F) Additive: N-2-(aminoethyl)-8-aminooctyltrimethoxysilane (KBM-6803, manufactured by Shin-Etsu)

[0202] Experimental Example: Evaluation of Pattern Physical Properties

[0203] A 5×5 cm glass substrate (Eagle 2000; manufactured by Corning) was sequentially cleaned with a neutral detergent, water, and alcohol, and then dried. The photosensitive resin compositions prepared in the above examples and comparative examples were each spin-coated onto the glass substrate, and then pre-baked at 85°C for 120 seconds using a hot plate. After cooling the pre-baked substrate to room temperature, light was irradiated with an exposure amount of 30 mJ / cm² (based on 365 nm) using an exposure machine (MPA-600FA; manufactured by Canon) with a distance of 50 μm from a quartz glass photomask.

[0204] At this time, a photomask was used having square openings (hole patterns) of a 5-20 μm square pattern and patterns formed on the same plane with mutual spacing of 100 μm. After light irradiation, the pattern was formed on the photosensitive resin composition film by developing in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 60 seconds, washing with ultrapure water, and drying under nitrogen. Post-bake was performed in an oven at 85 °C for 2 hours.

[0205] The following (1) to (7) physical property evaluations were performed on the above pattern, and the results are shown in Table 3 below.

[0207] (1) Residue evaluation

[0208] The presence of residue in the above-mentioned manufactured pattern (Hole pattern) was observed using an optical microscope (LV100POL, NIKON), and the residue was evaluated according to the following criteria, and the results are shown in Table 3 below.

[0209] <Evaluation Criteria>

[0210] No residue: ○

[0211] Residue present: X

[0213] (2) Heat resistance evaluation

[0214] The above-mentioned manufactured pattern was stored in an oven at a temperature of 85°C for 1 hour, and the change in film thickness before and after storage was measured. Heat resistance was evaluated according to the following criteria, and the results are shown in Table 3 below.

[0215] <Heat Resistance Evaluation Criteria>

[0216] ◎: Film thickness change less than 1%

[0217] ○: Film thickness change 1% or more, less than 2%

[0218] △: Film thickness change 2% or more, less than 5%

[0219] X: Film thickness change of 5% or more

[0221] (3) Alkali resistance evaluation

[0222] The above-described pattern was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 5 minutes, and the change in film thickness before and after immersion was measured. Alkali resistance was evaluated according to the following criteria, and the results are shown in Table 3 below.

[0223] Alkali Resistance Evaluation Criteria

[0224] ◎: Film thickness change less than 1%

[0225] ○: Film thickness change 1% or more, less than 2%

[0226] △: Film thickness change 2% or more, less than 5%

[0227] X: Film thickness change of 5% or more

[0229] (4) Evaluation of chemical resistance (change in film thickness)

[0230] The change in thickness of the above patterns was measured before and after immersing each pattern in an NMP aqueous solution for 6 minutes.

[0232] (5) Adhesion evaluation

[0233] For the adhesion evaluation of the cured film obtained above, a cross-cut test was conducted, and the results were expressed as ASTM Class.

[0235] (6) Scratch evaluation

[0236] Surface scratch evaluation of the cured coating obtained above was conducted using steel wool. The steel wool used was of the #0000s level, and a load of 1.5 kg was applied, with the test repeated 10 times at a speed of 60 revolutions per minute. After the evaluation, the coating was tested under darkroom conditions.

[0237] The number of scratches was counted under fluorescent light, and the number of scratches on the surface was evaluated according to the following criteria and summarized in Table 2 below.

[0238] < Surface Scratch Evaluation Criteria >

[0239] Fewer than 20 surface scratches: ○

[0240] 20 to 40 surface scratches: △

[0241] More than 40 surface scratches: X

[0243] (7) Evaluation of preservation stability

[0244] The photosensitive resin compositions prepared according to the above examples and comparative examples were placed in a 40°C oven, and the change in viscosity after 24 hours was evaluated and is shown in Table 3 below.

[0245] <Evaluation Criteria>

[0246] ◎: Viscosity change less than 1%

[0247] ○: Viscosity change 1% or more and less than 2%

[0248] △: Viscosity change 2% or more and less than 5%

[0249] X: Viscosity change of 5% or more

[0251] Residue heat resistance alkali resistance Chemical resistance (㎛) Adhesion scratch Conservation stability Example 1 ◎ ◎ ○ 0.00 5B ◎ ◎ Example 2 ◎ ◎ ○ -0.01 5B ◎ ◎ Example 3 ◎ ◎ ○ -0.03 5B ◎ ◎ Example 4 ○ ◎ ○ -0.01 5B ◎ ◎ Example 5 ○ ◎ ○ 0.02 5B ◎ ◎ Example 6 ◎ ○ ◎ -0.05 4B ○ ○ Example 7 ◎ ○ ◎ 0.07 4B ○ ○ Example 8 ◎ ○ ◎ -0.08 4B ○ ○ Example 9 ◎ ◎ ◎ 0.01 5B ○ ○ Example 10 ◎ ○ ○ -0.10 4B ◎ ◎ Example 11 ○ ◎ ◎ -0.04 4B ◎ ◎ Example 12 ○ ◎ ◎ -0.02 4B ◎ ◎ Comparative Example 1 △ ○ △ -0.35 1B X ○ Comparative Example 2 ○ ○ △ -0.25 1B X ○ Comparative Example 3 ○ ○ X -0.69 1B X ○ Comparative Example 4 X △ X -0.7 0B X △ Comparative Example 5 X △ X 0.75 1B △ X Comparative Example 6 X △ △ 0.52 0B X △ Comparative Example 7 X X X -0.85 0B X ○

[0253] As shown in Table 3 above, it was experimentally confirmed that patterns manufactured using the photosensitive resin compositions of Examples 1 to 12 according to the present invention do not produce residue, have excellent environmental reliability such as heat resistance, alkali resistance, and chemical resistance, and physical reliability such as adhesion and scratch resistance, and have excellent storage safety.

[0254] On the other hand, in the case of Comparative Examples 1 to 6, residue was generated and reliability and storage stability were poor, so it was confirmed that they were unsuitable for use in pattern formation at low temperatures.

Claims

Claim 1 A photosensitive resin composition comprising (A) a photoinitiator, (B) a thiol compound containing an ether bond, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a solvent, wherein the (B) thiol compound containing an ether bond comprises one or more compounds selected from those represented by the following Chemical Formula 1 and Chemical Formula 2, and the (D) photopolymerizable compound comprises a urethane acrylate oligomer. [Chemical Formula 1] (In the above Chemical Formula 1, R1 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R2 to R4 are each independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with hydrogen or one or more thiol groups.)[Chemical Formula 2] (In the above Chemical Formula 2, R5 is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups, and R6 to R 10 Each is independently a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, substituted with hydrogen or one or more thiol groups. Claim 2 The photosensitive resin composition of claim 1, wherein the urethane acrylate oligomer is represented by the following chemical formula 3 [Chemical Formula 3] (In the above chemical formula 3, m is 1 to 10, X is an m+1 hydrocarbon group, Y is a straight-chain alkylene group having 6 to 13 carbon atoms, an alkylene group including a saturated hydrocarbon ring structure, or an alkylene group including an aromatic ring structure, R 11 and R 12 Each is independently a hydrogen or a methyl group.) Claim 3 A photosensitive resin composition according to claim 1, wherein the thiol compound containing the ether bond is represented by the following formula 4 or formula 5: [Formula 4] (In the above chemical formula 4, R 13 is an alkylene group having 1 to 10 carbon atoms, m1 and n1 are each independently integers from 1 to 3, and m1 + n1 = 4. [Chemical Formula 5] (In the above chemical formula 5, R 14 Each is independently an alkylene group having 1 to 10 carbon atoms, and m2, m3, n2, and n3 are each independently integers from 1 to 3, m2+n2=3, and m3+n3=3.) Claim 4 A photosensitive resin composition according to claim 1, wherein the thiol compound containing the ether bond is represented by any one of the following chemical formulas A-1 to A-3. [Chemical formula A-1] [Chemical Formula A-2] [Chemical Formula A-3] Claim 5 A photosensitive resin composition according to claim 1, wherein the urethane acrylate oligomer comprises one or more of the following chemical formulas D-1 to D-3. [Chemical Formula D-1] [Chemical Formula D-2] [Chemical Formula D-3] Claim 6 A photosensitive resin composition according to claim 1, comprising, based on the total weight of the photosensitive resin composition: (A) 0.05 to 20 weight% of a photoinitiator; (B) 0.01 to 25 weight% of a thiol compound containing an ether bond; (C) 1 to 80 weight% of an alkali-soluble resin; (D) 1 to 80 weight% of a photopolymerizable compound; and (E) 10 to 90 weight% of a solvent. Claim 7 A photosensitive resin composition according to claim 1, further comprising an additive. Claim 8 A photosensitive resin composition according to claim 1, characterized in that the photosensitive resin composition is cured at 100°C or lower. Claim 9 A pattern comprising a cured product of the photosensitive resin composition of claim 1. Claim 10 In claim 9, the pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern including a scatterer, and a pattern including a quantum dot. Claim 11 A display device comprising the pattern of claim 10.

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