Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern

Abstract

A photosensitive resin composition according to the embodiments of the present disclosure comprises an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable compound, and a solvent. The photopolymerizable compound comprises a first monomer having a molecular weight of 550 g / mol or more and being a (meth)acrylate-based compound with 5 or more functional groups, and a second monomer having a molecular weight of less than 550 g / mol or being a (meth)acrylate-based compound with 4 or fewer functional groups. The content of the first monomer in the total weight of the photopolymerizable compound is greater than or equal to the content of the second monomer.

Description

Technology Field

[0001] The present invention provides a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device. Background Technology

[0003] In the field of displays, photosensitive resin compositions are used to form various photocurable patterns such as photoresists, insulating films, protective films, black matrices, and column spacers. For example, a desired photocurable pattern can be formed by selectively exposing and developing a photosensitive resin composition through a photolithography process.

[0004] Photosensitive resin compositions are classified into positive and negative types depending on the photocuring type. The photoresist formed by the positive type composition undergoes a change in the chemical structure of the exposed area and dissolves in the developer, whereas the photoresist formed by the negative type composition either hardens as the degree of polymerization of the exposed area increases or remains undissolved during the development process. The positive and negative type compositions may each include different binder resins, crosslinking agents, etc.

[0005] Recently, the use of touch screens equipped with touch panels has increased, and accordingly, display devices including flexible touch screens are being actively developed. Therefore, manufacturing processes for providing flexible polymer materials are also required to be carried out under milder low-temperature conditions. The problem to be solved

[0007] One objective of the present invention is to provide a photosensitive resin composition capable of realizing a highly durable pattern.

[0008] One objective of the present invention is to provide a highly durable photocurable pattern.

[0009] One objective of the present invention is to provide an image display device including the above-mentioned photocuring pattern. means of solving the problem

[0011] 1. A photopolymerizable compound comprising a first monomer having a molecular weight of 550 g / mol or more and being a (meth)acrylate-based compound with 5 or more functional groups, and a second monomer having a molecular weight of less than 550 g / mol or being a (meth)acrylate-based compound with 4 or fewer functional groups; an alkali-soluble resin; a photopolymerization initiator; and a solvent, wherein the content of the first monomer in the total weight of the photopolymerizable compound is greater than or equal to the content of the second monomer.

[0012] 2. A photosensitive resin composition according to 1, wherein the ratio of the content of the first monomer to the content of the second monomer in the total weight of the photopolymerizable compound is 1 to 9.

[0013] 3. A photosensitive resin composition according to 1, wherein the first monomer is at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol(meth)acrylate, and polypentaerythritol(meth)acrylate.

[0014] 4. A photosensitive resin composition according to 1, wherein the second monomer is at least one selected from the group consisting of a (meth)acrylate-based compound having four or fewer functions and a (meth)acrylate-based compound having five or more functions and a molecular weight of less than 550 g / mol.

[0015] 5. A photosensitive resin composition according to 1, wherein the content of the first monomer is 40% by weight or more of the total weight of the solids excluding the coloring agent in the composition, and the content of the second monomer is 20% by weight or less of the total weight of the solids excluding the coloring agent in the composition.

[0016] 6. A photosensitive resin composition according to 1, wherein the content of the photopolymerizable compound is 50% to 90% by weight of the total weight of the solids excluding the coloring agent in the composition.

[0017] 7. A photosensitive resin composition according to 1, wherein the alkali-soluble resin comprises a monomer comprising at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a glycidyl group, and an imide group.

[0018] 8. A photosensitive resin composition according to 1, wherein the content of the alkali-soluble resin is 10% to 50% by weight of the total weight of the solids excluding the coloring agent in the composition.

[0019] 9. A photosensitive resin composition according to 1, further comprising a coloring agent comprising at least one coloring pigment selected from the group consisting of a yellow pigment and a green pigment.

[0020] 10. A photosensitive resin composition according to 9, wherein the content of the coloring agent is 5% to 45% by weight of the total weight of the solid content of the composition.

[0021] 11. A photocured pattern formed from the photosensitive resin composition of 1 above.

[0022] 12. The photocuring pattern of 11, provided as a color filter, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, or a spacer pattern.

[0023] 13. An image display device including the photocuring pattern of 11 above. Effects of the invention

[0025] The photosensitive resin composition according to exemplary embodiments of the present invention may have low bottom penetration. For example, penetration of the photosensitive resin composition into the underlying film after a developing process and / or a peeling process may be suppressed, thereby reducing the rate of change in the thickness of the underlying film.

[0026] The photosensitive resin composition according to exemplary embodiments of the present invention can have high adhesion to the underlying substrate even after development. In addition, the chemical resistance, heat resistance, and degree of curing of the photocured pattern can be enhanced. Accordingly, surface damage, swelling, film shrinkage, etc., of the photocured pattern do not occur, so a high-quality image display device can be realized.

[0027] The photosensitive resin composition according to exemplary embodiments of the present invention may have improved hole-forming characteristics. Accordingly, the precision of the pattern can be improved so that fine patterns can be realized, and the degree of curing, durability, and uniformity of the pattern can be enhanced. Specific details for implementing the invention

[0029] The photosensitive resin composition of the present invention comprises a photopolymerizable compound comprising a (meth)acrylate-based monomer, an alkali-soluble resin, a photopolymerization initiator, and a solvent. Additionally, according to one embodiment of the present invention, a photocurable pattern formed by the photosensitive resin composition and an image display device including the same are provided.

[0030] In this specification, "(meth)acrylate" means including both acrylate and methacrylate.

[0031] The present invention will be described in detail below. However, this is merely illustrative and the present invention is not limited to the specific embodiments described illustratively.

[0032] A photosensitive resin composition according to exemplary embodiments comprises a photopolymerizable compound comprising a first monomer and a second monomer, which are (meth)acrylate-based compounds. The photopolymerizable compound may refer to a monomer comprising one or more polymerizable unsaturated bonds. The photopolymerizable compound may be cross-linked by a photopolymerization initiator described below to form a cured network. Accordingly, the degree of curing and density of a photocured pattern produced from the photosensitive resin composition may be enhanced.

[0033] For example, the first monomer and the second monomer may include a group represented by the following chemical formula 1 or chemical formula 2.

[0034] [Chemical Formula 1]

[0035]

[0036] [Chemical Formula 2]

[0037]

[0038] Among the above chemical formulas 1 and 2, * is a connection point.

[0039] For example, the group represented by the above Chemical Formula 1 and / or Chemical Formula 2 can form a curing network within the photopolymerizable compound.

[0040] According to exemplary embodiments, the first monomer is a (meth)acrylate-based compound having a molecular weight of 550 g / mol or more and having five or more functional groups. The first monomer can enhance the degree of curing and suppress the formation of uncured patterns.

[0041] For example, the first monomer may be at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol(meth)acrylate, and polypentaerythritol(meth)acrylate.

[0042] In some embodiments, the photopolymerizable compound may comprise two or more different first monomers. For example, the photopolymerizable compound may comprise two or more different first monomers selected from the (meth)acrylate-based compounds described above. Accordingly, a more uniform curing network may be formed, and the degree of curing may be enhanced.

[0043] According to exemplary embodiments, the second monomer is a (meth)acrylate-based compound with a molecular weight of less than 550 g / mol or four or fewer functionalities. For example, the photopolymerizable compound may include the second monomer to provide enhanced hole-forming properties.

[0044] For example, the density of the curing network can be controlled by the second monomer. Accordingly, when the photosensitive resin composition is exposed to light, the curing of the unexposed portion is further suppressed, and the hole formation characteristics can be improved. For example, the hole formation characteristics can determine the resolution of the fine patterning.

[0045] For example, when the photosensitive resin composition is applied to a substrate and a mask is placed for exposure, curing may occur even in the unexposed areas, which may reduce the resolution of the patterning. According to exemplary embodiments, the photopolymerizable compound may include a second monomer to provide improved hole-forming characteristics.

[0046] In some embodiments, the second monomer may be at least one selected from the group consisting of (meth)acrylate compounds with four or fewer functions and (meth)acrylate compounds with five or more functions and a molecular weight of less than 550 g / mol.

[0047] In one embodiment, the second monomer may include, for example, a monofunctional or 2 to 4-functional ethylenically unsaturated bond-containing compound.

[0048] For example, monofunctional ethylenically unsaturated bond-containing compounds may include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.

[0049] For example, difunctional ethylenically unsaturated compounds may 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.

[0050] For example, a 3 to 4-functional (meth)acrylate compound may be at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0051] In one embodiment, the photopolymerizable compound may include two or more different second monomers. Accordingly, the cured network can be formed more uniformly.

[0052] For example, the second monomer may be a (meth)acrylate-based compound with a molecular weight of 500 g / mol, 450 g / mol or less, 400 g / mol or less, 350 g / mol or less, or 300 g / mol or less. Within the above range, the hole-forming characteristics of the photocurable pattern prepared from the composition may be further improved.

[0053] According to exemplary embodiments, the content of the first monomer in the total weight of the photopolymerizable compound is greater than or equal to the content of the second monomer. Accordingly, the cured network can be further strengthened, thereby suppressing the formation of uncured patterns. Additionally, the penetration of uncured patterns into the underlying membrane can be further suppressed by bulky monomers having large molecular weights.

[0054] For example, if the content of the first monomer is smaller than the content of the second monomer, the cured network may not be sufficiently formed. Consequently, uncured patterns increase and penetrate into the underlying substrate, which may increase the thickness of the underlying film.

[0055] According to embodiments of the present disclosure, the content of the first monomer is controlled to be greater than or equal to the content of the second monomer, thereby improving the degree of curing, heat resistance, and chemical resistance of the photocuring pattern, while suppressing penetration of the underlying film, thereby reducing penetration of the underlying film and improving reworkability.

[0056] According to some embodiments, the ratio of the content of the first monomer to the content of the second monomer included in the photopolymerizable compound may be 1 to 15, 1 to 12, 1 to 9, 2 to 9, or 3 to 8. Within the above range, the degree of curing, heat resistance, chemical resistance, and reworkability of the photocuring pattern may be further enhanced.

[0057] In some embodiments, the content of the first monomer may be 40% by weight or more of the total weight of the solids excluding the coloring agent in the composition. In one embodiment, the content of the first monomer may be 40% to 90% by weight, 45% to 80% by weight, 50% to 75% by weight, or 55% to 70% by weight of the total weight of the solids excluding the coloring agent in the composition.

[0058] In some embodiments, the content of the second monomer may be 20% by weight or less of the total weight of the solids excluding the coloring agent in the composition. In one embodiment, the content of the second monomer may be 0.1% to 20% by weight, 1% to 20% by weight, or 3% to 18% by weight, or 5% to 15% by weight of the total weight of the solids excluding the coloring agent in the composition.

[0059] Within the above range, adhesion to the lower substrate can be improved, while the durability of the pattern can be further enhanced.

[0060] The content of the above photopolymerizable compound may be about 50% to 90% by weight or 55% to 85% by weight of the total weight of the solids excluding the coloring agent in the photosensitive resin composition. Within the above range, the occurrence of residue of the photocuring pattern is suppressed, and a fine pattern can be realized.

[0061] In exemplary embodiments, the composition comprises an alkali-soluble resin. The alkali-soluble resin may be a component that imparts solubility to an alkaline developer used in the development process when forming a pattern. For example, the alkali-soluble resin may be used without particular limitation as long as it is capable of imparting solubility to an alkaline developer.

[0062] In some embodiments, the alkali-soluble resin may comprise a monomer comprising at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a glycidyl group, and an imide group. For example, the alkali-soluble resin may be (co)polymerized from a mixture of the monomers described above.

[0063] For example, the alkali-soluble resin may include an ethylene unsaturated monomer having a carboxyl group. Specific examples of the ethylene unsaturated monomer 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. These may be used alone or in combination of two or more types, and for example, the ethylene unsaturated monomer having a carboxyl group may include acrylic acid and / or methacrylic acid.

[0064] For example, the alkali-soluble resin may include an ethylene unsaturated monomer having a hydroxyl group. Specific examples of the ethylene unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc. These may be used alone or in combination of two or more, and for example, the ethylene unsaturated monomer having a hydroxyl group may include 2-hydroxyethyl (meth)acrylate.

[0065] For example, the alkali-soluble resin may include a monomer having a glycidyl group. Specific monomers having a glycidyl group include butylglycidyl ether, glycidylpropyl ether, glycidylphenyl ether, 2-ethylhexylglycidyl ether, glycidyl butyrate, glycidylmethyl ether, ethylglycidyl ether, glycidyl isopropyl ether, t-butylglycidyl ether, benzylglycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, arylglycidyl ether, glycidyl methacrylic acid ester, etc. These may be used alone or in combination of two or more, and for example, the compound having a glycidyl group may include butylglycidyl ether, arylglycidyl ether, and / or glycidyl methacrylic acid ester.

[0066] For example, the monomer containing the imide group may include a maleimide compound. Examples of the maleimide compound may include 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.

[0067] For example, the alkali-soluble resin may include other unsaturated monomers. Examples of the other unsaturated monomers 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; 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; It may include aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; and 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. These may be used alone or in combination of two or more types.

[0068] In one embodiment, the alkali-soluble resin may comprise a copolymer copolymerized from a mixture of at least two different ethylenically unsaturated monomers. Accordingly, the adhesion and durability of the photocuring pattern can be further enhanced.

[0069] The acid value of the alkali-soluble resin may be 20 mgKOH / g to 200 mgKOH / g. In some embodiments, the acid value of the alkali-soluble resin may be 30 mgKOH / g to 150 mgKOH / g. When the acid value of the alkali-soluble resin satisfies the above range, the photosensitive resin composition can secure a sufficient development speed and improve adhesion to the substrate, thereby preventing the occurrence of short circuits in the pattern.

[0070] The weight average molecular weight (Mw) of the alkali-soluble resin may be 3,000 to 30,000. In some embodiments, the weight average molecular weight (Mw) of the alkali-soluble resin may be 5,000 to 25,000. Within this range, a photocurable pattern having excellent developability can be realized.

[0071] The content of the alkali-soluble resin may be 1% to 50% by weight of the total weight of the solids excluding the coloring agent in the composition. In some embodiments, the content of the alkali-soluble resin may be 1% to 45% by weight, 3% to 40% by weight, or 5% to 40% by weight of the total weight of the solids excluding the coloring agent in the composition. Within the above range, the chemical resistance, heat resistance, alkali resistance, etc. of the photocuring pattern may be further improved.

[0072] The above composition may include a photopolymerization initiator to induce a crosslinking reaction of the above-described photopolymerizable compound and provide curing pattern characteristics. The photopolymerization initiator may include a compound widely used in the field that can induce a crosslinking reaction of the above-described ethylenically unsaturated bond (e.g., (meth)acrylate)).

[0073] In some embodiments, the photopolymerization initiator may comprise a compound comprising a carbazole unit or a fluorene unit. For example, the photopolymerization initiator may be an oxime ester-based initiator comprising a carbazole unit or a fluorene unit. In this case, deep curing of the photocuring pattern can be promoted more effectively even in a low-temperature process.

[0074] By using the aforementioned photopolymerization initiator, degradation of exposure / development characteristics and resolution for fine pattern formation caused by the use of the alkali-soluble resin can be suppressed, and the reliability of the photocured pattern can be improved.

[0075] The above photopolymerization initiator may further include additional initiators widely used in the field that can induce a cross-linking reaction of the aforementioned ethylenically unsaturated bond-containing compound.

[0076] The above additional photopolymerization initiator may include acetophenone-based initiators, benzophenone-based initiators, benzoin-based initiators, thioxantone-based initiators, triazine-based initiators, oxime-based initiators, etc.

[0077] Examples of the above-mentioned acetophenone-based initiators 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.

[0078] Examples of the above-mentioned benzoin-based initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.

[0079] Examples of the above-mentioned benzophenone-based initiators include benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0080] Examples of the above-mentioned thioxantone-based initiators include 2-isopropylthioxantone, 2,4-diethylthioxantone, 2,4-dichlorothioxantone, and 1-chloro-4-propoxythioxantone.

[0081] Examples of the above triazine-based initiators include 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-piperonyl-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, and 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine. Examples include 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0082] Examples of the above-mentioned oxime-based initiators include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include BASF's OXE-01 and OXE-02.

[0083] In one embodiment, the black photosensitive resin composition may further include a photopolymerization initiation aid. The photopolymerization initiation aid promotes the polymerization of a photopolymerizable compound and can be used together with a photopolymerization initiator.

[0084] For example, the above photopolymerization initiation aid may include amine-based initiation aids, alkoxyanthracene-based photopolymerization initiation aids, etc.

[0085] The content of the photopolymerization initiator may be 5% to 30% by weight of the total weight of the solids excluding the coloring agent in the composition. According to some embodiments, the content of the photopolymerization initiator may be 8% to 25% by weight or 10% to 20% by weight of the total weight of the solids excluding the coloring agent in the composition. Within the above range, the curability of the photocuring pattern is improved, while preventing the detachment of the pattern during the development process and preventing the occurrence of wrinkles caused by excessive cross-linking reactions.

[0086] The above solvent may include an organic solvent that has solubility for the alkali-soluble resin described above and can provide coating properties for the photosensitive resin composition.

[0087] For example, ether-based solvents, acetate-based solvents, aromatic hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents and / or ester-based solvents may be used.

[0088] Examples of the above ether-based solvents include ethylene glycol monoalkyl ether compounds, diethylene glycol dialkyl ether compounds, propylene glycol monomethyl ether, etc.

[0089] Examples of the above acetate-based solvents include methyl cellosolve acetate, ethyl cellosolve acetate, alkyl acetate, alkoxyalkyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoalkyl ether acetate, etc.

[0090] Examples of the above aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.

[0091] Examples of the above-mentioned ketone-based solvents include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.

[0092] Examples of the above alcohol-based solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 4-hydroxy-4-methyl-2-pentanone, etc.

[0093] The amount of the above solvent can be appropriately adjusted considering the sufficient solubility of components such as the above alkali-soluble resin and the coating properties of the composition, and may be included as the remainder of the above photosensitive resin composition.

[0094] The term "residual amount" as used in this application is used in an open sense, adjusted according to components or additives added in variable amounts.

[0095] In exemplary embodiments, the content of the solvent may be 50% to 95% by weight of the total weight of the photosensitive resin composition. In some embodiments, the content of the solvent may be 60% to 90% by weight, or 70% to 90% by weight, of the total weight of the photosensitive resin composition. Within these ranges, the applicability may be improved when applied using an application device such as a roll coater, spin coater, slit-and-spin coater, slit coater, inkjet, etc.

[0096] According to exemplary embodiments, the photosensitive resin composition may further include other additives.

[0097] Examples of other additives may be considered, such as antioxidants including 2,2'-thiobis(4-methyl-6-t-butylphenol) or 2,6-di-t-butyl-4-methylphenol; curing agents including epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, or oxetane compounds; curing aids including polycarboxylic acids or polycarboxylic acid anhydrides; surfactants including silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, or amphoteric surfactants; adhesion promoters including trialkoxysilane compounds containing vinyl groups, halogens, isocyanate groups, thiol groups, primary to tertiary amine groups, etc.; and anti-coagulation agents such as sodium polyacrylate.

[0098] The content of the above other additives may be 0.01 to 10 weight percent of the total weight of the photosensitive resin composition, and the content may be controlled within a range where the physical properties of the photocured pattern formed from the photosensitive resin composition are not degraded.

[0099] In some embodiments, the photosensitive resin composition may further include a coloring agent. Accordingly, a photocurable pattern formed from the composition may be provided as a color filter.

[0100] For example, the coloring pigments are yellow pigments such as CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as CI Pigment Green 7, 36, 58, 59; brown pigments such as CI Pigment Brown 23, 25; or CI Pigment Black Examples include black pigments such as 1, 7, lactam black, and carbon black.

[0101] In one embodiment, the coloring agent may include at least one coloring pigment selected from the group consisting of the yellow pigment and the green pigment.

[0102] The content of the coloring agent may be 5% to 45% by weight, 5% to 30% by weight, or 10% to 10% by weight of the total weight of the solids of the composition. Within the above range, the optical density, resolution, etc. of the photocured pattern may be further improved.

[0103] In some embodiments, the pigment may be used together with a pigment dispersant. The pigment dispersant may be added together with the pigment to suppress the aggregation of the pigment and enhance dispersion properties.

[0104] Examples of the above pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants.

[0105] For example, the content of the pigment dispersant may be included in an amount of 5% to 50% by weight relative to the total weight of the solid content of the pigment. Within this range, excessive viscosity increase can be suppressed, and the aggregation of the pigment and gelation of the composition can be prevented.

[0106] The present invention provides a photocurable pattern formed from the above photosensitive resin composition.

[0107] The above photocuring pattern may be, for example, a color filter further comprising a coloring agent, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.

[0108] For example, a photosensitive resin composition according to each exemplary embodiment can be applied to a substrate and then dried to obtain a coating film.

[0109] Examples of coating methods may include spin coating, flexible coating, roll coating, slit-and-spin coating, or slit coating. Additionally, the solvent may be dried and removed through heat drying (pre-baking) or vacuum drying. The heating temperature may typically be 70 to 150°C or 80 to 130°C.

[0110] A mask may be placed on one side of the above coating film, and ultraviolet rays may be irradiated to form a pattern. Before irradiating with ultraviolet rays, a device such as a mask aligner or a stepper may be installed. The irradiated area may be cured by irradiating with ultraviolet rays.

[0111] The above ultraviolet light is 10 mJ / cm² 2 Up to 50 mJ / cm² 2 It can be irradiated with an intensity of , and g-lines (wavelength: 436 nm), h-lines, i-lines (wavelength: 365 nm), etc., may be used. The amount of ultraviolet irradiation can be appropriately selected by a person skilled in the art as needed.

[0112] After light irradiation, if the above coating film is exposed to an alkaline developer, the coating film in the uncured area (non-exposed area) may be dissolved, and a photocured pattern may be developed through the dissolution.

[0113] As examples of development methods, the liquid addition method, dipping method, and spray method may be considered, and the substrate may be tilted at an arbitrary angle during development.

[0114] The alkaline developer used for developing a photocured pattern according to an exemplary embodiment may include an alkaline compound. Non-limiting examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, etc., and organic alkaline compounds such as triethylamine, tetramethylammonium hydroxide, ethanolamine, etc.

[0115] The above developer may further include a surfactant. As non-limiting examples of the above surfactant, known nonionic surfactants, anionic surfactants, or cationic surfactants may be considered.

[0116] In addition, according to exemplary embodiments, an image display device including the photocurable pattern is provided.

[0117] In an image display device according to exemplary embodiments, the photocuring pattern may include a color filter further comprising a coloring agent, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern and / or a spacer pattern, etc.

[0118] In addition, as examples of the above-mentioned image display devices, liquid crystal displays (LCDs), organic EL displays (organic EL displays), liquid crystal projectors, display devices for game consoles, display devices for mobile terminals such as mobile phones, display devices for digital cameras, display devices for car navigation, etc. may be considered.

[0119] In addition, the image display device may include other components that can typically be included in an image display device, such as a light-emitting device like a light source, a light guide plate, and a liquid crystal display unit including a color filter.

[0120] In the following, embodiments of the present invention are further described with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples 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 that such variations and modifications fall within the scope of the appended claims.

[0122] Synthesis Example: Preparation of alkali-soluble resin (B)

[0123] 180 parts by weight of propylene glycol monomethyl ether acetate and 20 parts by weight of propylene glycol monomethyl ether were placed in a flask equipped with a stirrer, thermometer, reflux condenser, dropping lot, and nitrogen inlet tube, and the atmosphere inside the flask was replaced with nitrogen. After heating the flask to 90°C, 30 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl maleimide, 40 parts by weight of methyl methacrylate, 10 parts by weight of cyclohexyl methacrylate, and 5 parts by weight of 2,2'-azobis isobutyronitrile (Wako) were added, and polymerization was carried out for 6 hours. After cooling to room temperature and replacing the atmosphere inside the flask with air, 55 parts by weight of glycidyl methacrylate and 4 parts by weight of n-dodecanethiol were added, the temperature was raised to 80°C and reacted for 12 hours to obtain an alkali-soluble resin (B) (solid content: 10 wt%). The solid-dispersion acid value of the alkali-soluble resin (B) was 130 mgKOH / g, and the weight-average molecular weight (Mw) of the solid content, calculated by standard polystyrene conversion, was approximately 9,000 g / mol.

[0125] Examples and Comparative Examples

[0126] A photosensitive resin composition was prepared by adjusting the types and content of the components as described in Table 1 below. The content of each component is in weight% of the total weight of the composition.

[0127] division (A) (B) (C) (D) (E) (C-1) (C-2) Content Content type Content type Content Content Content Example 1 5.5 3.5 C-1-1 5.0 C-2-1 1.0 2 83 Example 2 5.5 3.5 C-1-2 5.0 C-2-1 1.0 2 83 Example 3 5.5 3.5 C-1-3 5.0 C-2-1 1.0 2 83 Example 4 5.5 3.5 C-1-1 5.0 C-2-2 1.0 2 83 Example 5 5.5 3.5 C-1-1 5.0 C-2-3 1.0 2 83 Example 6 5.5 3.5 C-1-1 5.0 C-2-4 1.0 2 83 Example 7 5.5 4.5 C-1-1 4.0 C-2-1 1.0 2 83 Example 8 5.5 2.5 C-1-1 6.0 C-2-1 1.0 2 83 Example 9 5.5 3.5 C-1-1 4.0 C-2-1 2.0 2 83 Example 10 5.5 3.5 C-1-1 3.0 C-2-1 3.0 2 83 Example 11 5.5 4.0 C-1-1 5.0 C-2-1 0.5 2 83 Example 12 5.5 2.0 C-1-1 7.0 C-2-1 0.5 2 83 Example 13 5.5 2.0 C-1-1 / C-1-2 3.2 / 3.3 C-2-1 1.0 2 83 Comparative Example 1 5.5 4.5 C-1-1 5.0 - - 2 83 Comparative Example 2 5.5 6.5 C-1-1 3.0 - - 2 83 Comparative Example 3 5.5 4.5 - - C-2-1 5.0 2 83 Comparative Example 4 5.5 4.5 - - C-2-2 5.0 2 83 Comparative Example 5 5.5 4.5 - - C-2-4 5.0 2 83 Comparative Example 6 5.5 3.5 - - C-2-1 6.0 2 83 Comparative Example 7 5.5 4.5 C-1-1 1.5 C-2-1 3.5 2 83

[0128] (A) Colorant: A mixture of CI Pigment Green 7 (G7) and CI Pigment Yellow 150 (Y150) (weight ratio = 7:3)

[0129] (B) Alkali-soluble resin: Alkali-soluble resin of the above synthesis example

[0130] (C) Photopolymerizable compound

[0131] (C-1) First monomer

[0132] C-1-1: A-9550 (5-6 functional (meth)acrylate, molecular weight 551.54, Shinnakamura)

[0133] C-1-2: A-9570 (5-6 functional (meth)acrylate, molecular weight 551.54, Shinnakamura)

[0134] C-1-3: A-DPH-12E (5-6 cell functional (meth)acrylate, molecular weight 1593, Shinnakamura)

[0135] (C-2) Second monomer

[0136] C-2-1: A-TMM-3LM-N (3~4 functional (meth)acrylate, molecular weight 319.91, Shinnakamura)

[0137] C-2-2: ATM-4E (tetrafunctional (meth)acrylate, molecular weight 528.5, Shinnakamura)

[0138] C-2-3: A-DPH (pentafunctional (meth)acrylate, molecular weight 520, Shinnakamura)

[0139] C-2-4: A-TMPT (trifunctional (meth)acrylate, molecular weight 296.32, Shinnakamura)

[0140] (D) Photopolymerization initiator: OXE-02 (Basf)

[0141] (E) Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

[0143] Experimental example

[0144] A 5 cm × 5 cm glass substrate (#1737, manufactured by Corning) was sequentially cleaned with a neutral detergent, water, and alcohol, and then dried. The photosensitive resin compositions of the example and comparative example were each spin-coated onto the glass substrate, and then placed in a heating oven and pre-baked at 100°C for 3 minutes to form a film on the substrate.

[0145] A test photomask having a line pattern with a width ranging from 1 μm to 100 μm is placed on the above coating film, and 80 mJ / cm² is applied under atmospheric conditions using an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio Denki Co., Ltd.).2 Light was irradiated with an exposure amount (based on 365 nm).

[0146] After light irradiation, an aqueous KOH solution with a pH of 12.5 was developed using a spray developer for 70 seconds. The sample was dried under a nitrogen atmosphere and post-baked in an oven at 100°C for 60 minutes to form a photocured pattern. The thickness of the prepared photocured pattern was 2.9 μm.

[0147] The physical properties of the above photocuring pattern were evaluated according to the following evaluation method, and the results are shown in Table 2 below.

[0149] (1) Adhesion evaluation

[0150] The photocured pattern prepared in the experimental example was observed using an optical microscope, and the adhesion of the line pattern was evaluated as follows. Adhesion was evaluated as being superior when the size of the minimum pattern remaining on the coating film without defects after development was smaller.

[0151] <Closeness Evaluation Criteria>

[0152] ◎: Minimum pattern size is 3 µm or less

[0153] ○: Minimum pattern size is greater than 3 µm and less than or equal to 7 µm

[0154] △: Minimum pattern size greater than 7 µm and 10 µm or less

[0155] X: Minimum pattern size greater than 10 µm and 20 µm or less

[0157] (2) Chemical resistance evaluation

[0158] The substrate prepared in the experimental example was immersed in a petri dish containing a mixed solution of propylene glycol monomethyl ether acetate (PGMEA):propylene glycol monomethyl ether (PGME) (weight ratio = 8:2) and stirred for 2 minutes.

[0159] Chemical resistance was evaluated as follows by measuring the percentage change in film thickness before and after immersion based on the value obtained by subtracting the film thickness before immersion from the film thickness after immersion.

[0160] Chemical Resistance Evaluation Criteria

[0161] ◎: Film thickness change rate 3% or less

[0162] ○: Film thickness change rate exceeding 3% and 5% or less

[0163] △: Film thickness change rate exceeding 5% and 10% or less

[0164] X: Film thickness change rate exceeding 10%

[0166] (3) Hardness evaluation

[0167] The substrate prepared in the experimental example was immersed in a mixed solution of propylene glycol monomethyl ether acetate (PGMEA): ethyl 3-epoxypropionate (EEP) (weight ratio = 8:2) and left for 1 minute. Afterward, the substrate was washed with distilled water and dried under a nitrogen atmosphere.

[0168] The degree of curing was evaluated as follows by measuring the rate of change (%) of the film thickness before and after the above film was calculated by subtracting the film thickness before the film was left from the film thickness after the film was left.

[0169] Hardness Evaluation Criteria

[0170] ◎: Film thickness change rate 1% or less

[0171] ○: Film thickness change rate greater than 1% and 3% or less

[0172] △: Film thickness change rate exceeding 3% and 5% or less

[0173] Х : Film thickness change rate exceeding 5%

[0175] (4) Evaluation of lower permeability

[0176] The thickness of the coating film (underlayer) on the substrate prepared in the experimental example was measured. In addition, the photosensitive resin compositions of the examples and comparative examples were spin-coated again onto the substrate, and a coating film was formed on the substrate by placing it in a heating oven and pre-baking it at 100°C for 3 minutes. The substrate was developed with a KOH aqueous solution with a pH of 12.5 using a spray developer for 70 seconds, washed with distilled water, and dried under a nitrogen atmosphere. The percentage change in film thickness of the underlayer before and after development was measured based on the value obtained by subtracting the thickness of the underlayer before development from the thickness of the underlayer after development, and the underlayer penetration was evaluated as follows. The lower the percentage change in film thickness (%), the better the underlayer penetration was evaluated.

[0177] <Subsurface Penetration Assessment>

[0178] ◎: Film thickness change rate 3% or less

[0179] ○: Film thickness change rate exceeding 3% and 4% or less

[0180] △: Film thickness change rate exceeding 4% and 7% or less

[0181] Х : Film thickness change rate exceeding 7%

[0183] (5) Evaluation of hole formation characteristics

[0184] A photocuring pattern was formed in the same manner as in the experimental example, except that a mask with a hole of 7 μm in diameter was used instead of the test photomask.

[0185] Hole formation was evaluated by measuring the size of the hole formed on the substrate. The hole formation characteristics were evaluated as being superior as the hole size approached 7 μm.

[0186] <Evaluation Criteria for Hole Formation Characteristics>

[0187] ◎: Hole size is 4 µm to 7 µm

[0188] ○: Hole size is 2 µm or more and less than 4 µm

[0189] △: Hole size is 4 µm or less

[0190] Х : No hole formed

[0191] division Adhesion Chemical resistance Hardness Subsurface penetration Hole formation characteristics Example 1 ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ◎ ◎ ◎ Example 11 ○ ○ ○ ○ ○ Example 12 ○ ○ ○ ○ ○ Example 13 ◎ ◎ ◎ ◎ ◎ Comparative Example 1 ○ ○ ○ ○ × Comparative Example 2 ○ ◎ ○ ◎ × Comparative Example 3 △ △ ○ × ◎ Comparative Example 4 ○ ◎ ○ △ ◎ Comparative Example 5 △ × × × ◎ Comparative Example 6 ◎ ○ ◎ △ × Comparative Example 7 ◎ ○ ○ × ◎

[0192] Referring to Table 2 above, the photocurable patterns prepared from the photosensitive resin compositions of the examples including the first monomer and the second monomer showed improved adhesion, chemical resistance, and degree of curing compared to the comparative examples.

[0193] In the case of photocuring patterns prepared from photosensitive resin compositions of Comparative Examples 1 and 2 containing only the first monomer, the hole formation characteristics were excessively degraded.

[0194] In the case of photocured patterns prepared from photosensitive resin compositions of Comparative Examples 3 to 6 containing only the second monomer, the uncured pattern increased, and the chemical resistance and degree of curing decreased. In addition, the content of monomers with large molecular weights decreased, resulting in deterioration of bottom penetration.

[0195] In the case of a photocured pattern prepared from the photosensitive resin composition of Comparative Example 7, in which the content of the first monomer was controlled to be smaller than the content of the second monomer, the bottom penetration was deteriorated compared to the examples.

[0197] The description above is merely an example of applying the principles of the present invention, and other configurations may be included without departing from the scope of the present invention.

Claims

Claim 1 A photosensitive resin composition comprising: a photopolymerizable compound comprising a first monomer having a molecular weight of 550 g / mol or more and being a (meth)acrylate-based compound with 5 or more functional groups, and a second monomer having a molecular weight of less than 550 g / mol or being a (meth)acrylate-based compound with 4 or fewer functional groups; an alkali-soluble resin; a photopolymerization initiator; and a solvent, wherein the content of the first monomer in the total weight of the photopolymerizable compound is greater than or equal to the content of the second monomer. Claim 2 A photosensitive resin composition according to claim 1, wherein the ratio of the content of the first monomer to the content of the second monomer in the total weight of the photopolymerizable compound is 1 to 9. Claim 3 A photosensitive resin composition according to claim 1, wherein the first monomer is at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol(meth)acrylate, and polypentaerythritol(meth)acrylate. Claim 4 A photosensitive resin composition according to claim 1, wherein the second monomer is at least one selected from the group consisting of a (meth)acrylate-based compound having four or fewer functions and a (meth)acrylate-based compound having five or more functions and a molecular weight of less than 550 g / mol. Claim 5 A photosensitive resin composition according to claim 1, wherein the content of the first monomer is 40% by weight or more of the total weight of the solids excluding the coloring agent in the composition, and the content of the second monomer is 20% by weight or less of the total weight of the solids excluding the coloring agent in the composition. Claim 6 A photosensitive resin composition according to claim 1, wherein the content of the photopolymerizable compound is 50% to 90% by weight of the total weight of the solids excluding the coloring agent in the composition. Claim 7 A photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises a monomer having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a glycidyl group, and an imide group. Claim 8 A photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin is 10% to 50% by weight of the total weight of the solids excluding the coloring agent in the composition. Claim 9 A photosensitive resin composition according to claim 1, further comprising a coloring agent comprising at least one coloring pigment selected from the group consisting of a yellow pigment and a green pigment. Claim 10 A photosensitive resin composition according to claim 9, wherein the content of the coloring agent is 5% to 45% by weight of the total weight of the solid content of the composition. Claim 11 A photocurable pattern formed from the photosensitive resin composition of claim 1. Claim 12 A photocuring pattern according to claim 11, provided as a color filter, an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, or a spacer pattern. Claim 13 An image display device comprising the photocuring pattern of claim 11.

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