Photosensitive resin composition, pattern formed therefrom, and display device

Abstract

The present invention relates to a photosensitive resin composition, a pattern formed therefrom, and a display device, the photosensitive resin composition including an alkali-soluble resin containing a compound represented by Chemical Formula 1 polymerized, and a thiol compound containing an ether bond characterized by including one or more selected from compounds represented by Chemical Formula 2 and Chemical Formula 3, thereby enabling low-temperature curing, while having low dielectric properties and reagent resistance.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, patterns formed therefrom, and display devices. Background Technology

[0002] In the display industry, photosensitive resin compositions are used to form a wide variety of cured patterns, such as photoresists, insulating films, protective films, black matrices, and columnar spacers. Specifically, the photosensitive resin composition is selectively exposed and developed through a photolithography process to form the desired pattern. In this process, a highly sensitive photosensitive resin composition is required to improve process yield and enhance the physical properties of the application.

[0003] Specifically, the patterning of the photosensitive resin composition relies on photolithography, which involves polarity changes and cross-linking reactions of polymers caused by photoreaction. In particular, the patterning utilizes the change in solubility in solvents such as alkaline aqueous solutions after exposure.

[0004] The desired photocurable pattern is formed by selectively exposing and developing a photosensitive resin composition through a photolithography process. In order to improve the yield of the process and improve the physical properties of the application, a photosensitive resin composition with excellent chemical and physical properties is required.

[0005] In recent years, displays have also been developing towards flexible forms, thus advancing the development of flexible displays that can maintain their shape even when folded or rolled up without damage. Therefore, the materials that can be used are limited to flexible polymers, and the manufacturing process also needs to be carried out under milder, lower-temperature conditions.

[0006] Therefore, the curing conditions for photosensitive resin compositions have shifted from high-temperature curing to low-temperature curing. However, low-temperature curing conditions result in reduced reactivity and decreased durability of the formed pattern. Furthermore, it not only leads to reduced heat resistance but also causes problems in subsequent processes due to exposure to the solvents used, such as decreased chemical resistance (e.g., swelling due to surface penetration and reduced adhesion), pattern surface damage, and reduced adhesion to the underlying substrate.

[0007] Furthermore, for low-temperature curing organic insulating films to be used in large-area IT applications, low resistance characteristics are required to avoid slowing down the electrical signal speed of metal wiring. Currently researched organic insulating films have dielectric properties of ε=3.5 or higher, which does not meet this requirement. Additionally, insufficient reagent resistance in low-temperature processes prevents their practical application. In particular, regarding monomers included in inkjet compositions, some substances are known to have low dielectric constants, but their introduction into photosensitive resin compositions presents limitations that can lead to reliability issues.

[0008] Korean Patent Publication No. 10-2023-0020919 discloses a curable composition containing a compound with a specific structure, a cured film, a method for manufacturing the same, an organic EL element, a liquid crystal display element, a semiconductor element, a printed circuit board, and a polymer, all capable of producing films with low dielectric constants and good curability. However, to form the insulating film pattern, post-baking curing conditions above 230°C are required. This process may damage the ITO substrate, and there is a problem that it is not possible to simultaneously achieve low dielectric constant, process reliability, and reagent resistance under low-temperature curing conditions.

[0009] Therefore, there is an urgent need to develop a photosensitive resin composition that has low dielectric properties, excellent reagent resistance and reliability under low-temperature curing conditions, thereby benefiting its electrical properties.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Korean Patent Publication No. 10-2023-0020919 Summary of the Invention

[0013] The problem to be solved

[0014] In order to solve the above-mentioned technical problems, the present invention aims to provide a photosensitive resin composition having low dielectric properties and / or low refractive properties under low temperature curing conditions.

[0015] Furthermore, the object of the present invention is that the above-mentioned photosensitive resin composition has reagent resistance (chemical resistance) in low-temperature processes.

[0016] Furthermore, the object of the present invention is to provide a pattern and display device of excellent quality manufactured using the above-described photosensitive resin composition.

[0017] However, the problems to be solved by this application are not limited to those mentioned above, and those skilled in the art should be able to clearly understand other problems not mentioned based on the following description.

[0018] Methods for solving problems

[0019] The present invention relates to a photosensitive resin composition, characterized in that it comprises an alkali-soluble resin polymerized from a compound represented by the following chemical formula 1 and a thiol compound containing an ether bond, wherein the thiol compound containing the ether bond comprises one or more compounds selected from the compounds represented by the following chemical formulas 2 and 3.

[0020] [Chemical Formula 1]

[0021]

[0022] (In the above chemical formula 1, R1 is hydrogen or methyl, and R2 is an alkyl group or a cycloalkyl group with 12 to 21 carbon atoms.)

[0023] [Chemical Formula 2]

[0024]

[0025] [Chemical Formula 3]

[0026]

[0027] (In the above chemical formulas 2 and 3, R3 is each independently a thiol group (-SH) or one or more straight-chain or branched alkyl groups having 1 to 10 carbon atoms with the terminal substituted thiol group (-SH), and R4 to R6 are each independently hydrogen (H), thiol group (-SH) or one or more straight-chain or branched alkyl groups having 1 to 10 carbon atoms with the terminal substituted thiol group (-SH).)

[0028] The present invention is characterized in that R2 of the compound represented by the above chemical formula 1 may contain a branched structure.

[0029] In this invention, R2 of the compound represented by the above chemical formula 1 can be an alkyl group having 13 to 18 carbon atoms or a cycloalkyl group having 13 to 18 carbon atoms.

[0030] In this invention, the above-mentioned thiol compounds containing ether bonds can be represented by the following chemical formula 4 or chemical formula 5.

[0031] [Chemical Formula 4]

[0032]

[0033] (In the above chemical formula 4, R7 is an alkylene group with 1 to 10 carbon atoms, m1 and n1 are each independent integers from 1 to 3, and m1 + n1 = 4.)

[0034] [Chemical Formula 5]

[0035]

[0036] (In the above chemical formula 5, R8 is an alkylene group with 1 to 10 carbon atoms, m2, m3, n2 and n3 are each an integer from 1 to 3, and m2+n2=3, m3+n3=3.)

[0037] In this invention, the above-mentioned photosensitive resin composition may further contain one or more selected from photopolymerizable unsaturated monomers, photopolymerization initiators, and solvents.

[0038] The present invention is characterized in that the pattern made from the above-described photosensitive resin composition has a value of 3.25 or less after curing, calculated by the following formula 1.

[0039] [Mathematical Expression 1]

[0040] k = (C × A) / (εo × d)

[0041] In the above mathematical formula 1, k represents the dielectric ratio, C represents the capacitance, εo represents the vacuum dielectric constant, d represents the thickness of the thin film, and A represents the contact cross-sectional area of ​​the electrode.

[0042] The present invention is characterized in that the above-mentioned photosensitive resin composition can be cured at a temperature below 100°C.

[0043] In addition, the present invention relates to patterns of cured products comprising the above-mentioned photosensitive resin composition, wherein the patterns may be selected from the group consisting of array planarization film patterns, protective film patterns, insulating film patterns, photoresist patterns, black matrix patterns, columnar spacer patterns, black columnar spacers, colored resist patterns, patterns containing scatterers, and patterns containing quantum dots.

[0044] The present invention is characterized in that the refractive index of the above pattern can be 1.48 to 1.52 after curing.

[0045] In addition, the present invention relates to a display device incorporating the above-described pattern.

[0046] Invention Effects

[0047] The photosensitive resin composition of the present invention, by comprising an alkali-soluble resin and a thiol compound with a specific structure, exhibits low refractive index characteristics of 1.48 to 1.52. Even under low-temperature curing conditions below 100°C, it can produce cured products exhibiting low dielectric properties of 3.25 or lower, and can provide patterns with excellent physical properties such as excellent chemical resistance and no residue. Therefore, it can provide display devices with excellent electrical properties, improved surface uniformity of the pattern, and excellent reliability. Detailed Implementation

[0048] The present invention relates to a photosensitive resin composition comprising: an alkali-soluble resin polymerized from a compound represented by the following chemical formula 1; and a thiol compound containing an ether bond.

[0049] More specifically, in this invention, the thiol compound containing an ether bond may include one or more compounds selected from those represented by the following chemical formulas 2 and 3.

[0050] As described above, the present invention relates to a photosensitive resin composition comprising an alkali-soluble resin with a specific structure and a thiol compound containing an ether bond, thereby having low dielectric properties that enable low-temperature curing and exhibiting a low refractive index of 1.48 to 1.52, patterns formed therefrom, and display devices.

[0051] [Chemical Formula 1]

[0052]

[0053] In the above chemical formula 1, R1 is hydrogen or methyl, and R2 is an alkyl group with 12 to 21 carbon atoms or a cycloalkyl group with 12 to 21 carbon atoms.

[0054] [Chemical Formula 2]

[0055]

[0056] [Chemical Formula 3]

[0057]

[0058] In the above chemical formulas 2 and 3, R3 is each independently a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are straight-chain or branched and have 1 to 10 carbon atoms that are substituted with a thiol group (-SH) at the end, and R4 to R6 are each independently hydrogen (H), a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are straight-chain or branched and have substituted with a thiol group (-SH) at the end.

[0059] By manufacturing a product comprising the above-described photosensitive resin composition, it is possible to achieve patterns and display devices comprising the same, exhibiting a low dielectric constant of less than 3.5, preferably less than 3.25, and more preferably 2.5 to 2.6, even under low-temperature curing conditions below 100°C. This results in advantages such as improved insulation between metal wirings, enabling sensing sensitivity and high-resolution wiring. Furthermore, it possesses excellent physical properties, including chemical resistance, reagent resistance, and / or solvent resistance, and leaves no residue. In this invention, the low-temperature curing temperature can be referenced to the post-baking temperature. In particular, in one embodiment of the invention, by simultaneously comprising an alkali-soluble resin polymerized from a compound represented by Formula 1 and a thiol compound containing an ether bond, it is possible to achieve properties that improve resistance to reagents used in metal processing, thereby further enhancing product reliability.

[0060] Hereinafter, embodiments of the present invention are described in more detail. However, the terminology used in this specification is intended to describe the embodiments and is not intended to limit the invention. In this specification, the singular form also includes the plural form unless the context otherwise requires.

[0061] The terms “comprises” and / or “comprising” as used in this specification are used to mean, without excluding, one or more other constituent elements, steps and / or ingredients besides those mentioned.

[0062] <Photosensitive Resin Composition>

[0063] The photosensitive resin composition of the present invention comprises: an alkali-soluble resin polymerized from a compound represented by chemical formula 1; and a thiol compound containing an ether bond, characterized by comprising one or more compounds selected from those represented by chemical formulas 2 and 3. Additionally, it may also comprise one or more selected from photopolymerizable unsaturated monomers, photopolymerization initiators, and solvents.

[0064] [Chemical Formula 1]

[0065]

[0066] In the above chemical formula 1, R1 can be hydrogen or methyl, and R2 can be an alkyl group with 12 to 21 carbon atoms or a cycloalkyl group with 12 to 21 carbon atoms.

[0067] [Chemical Formula 2]

[0068]

[0069] [Chemical Formula 3]

[0070]

[0071] In the above chemical formulas 2 and 3, R3 can each independently be a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are straight-chain or branched and have 1 to 10 carbon atoms that are terminally substituted with a thiol group (-SH), and R4 to R6 can each independently be hydrogen (H), a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are terminally substituted with a thiol group (-SH).

[0072] Alkali-soluble resins

[0073] The photosensitive resin composition comprises an alkali-soluble resin, and the alkali-soluble resin of one embodiment of the present invention is characterized by being polymerized from a compound represented by the following chemical formula 1.

[0074] [Chemical Formula 1]

[0075]

[0076] In the above chemical formula 1, R1 can be hydrogen or methyl, and R2 can be an alkyl group with 12 to 21 carbon atoms or a cycloalkyl group with 12 to 21 carbon atoms. Preferably, R2 can be an alkyl group with 13 to 18 carbon atoms or a cycloalkyl group with 13 to 18 carbon atoms.

[0077] When the above-mentioned alkali-soluble resin contains the structural unit of the above-mentioned chemical formula 1, the photosensitive resin composition has a dielectric loss tangent value within a predetermined range, and thus exhibits the characteristics of an organic insulating film with low dielectric properties.

[0078] Furthermore, more specifically, compared to the straight chain, the R2 of the compound represented by the above chemical formula 1 is preferred to have a branched structure, which improves the compatibility between materials. Often, the longer the alkyl group is, the more hydrophobic it becomes, which leads to a worse compatibility between materials. Therefore, it has the advantage of simultaneously satisfying low dielectric properties and compatibility between materials within a predetermined range.

[0079] In addition to the compounds represented by Formula 1 above, the alkali-soluble resin of the present invention can also be manufactured by polymerizing various polymerizable compounds known in the art, as needed. For example, it can be a polymer obtained by further reacting a copolymer of a compound having carboxyl groups and unsaturated bonds with a compound having unsaturated bonds and glycidyl groups; preferably, it can be a polymer obtained by further reacting a polymer of a compound having unsaturated bonds and glycidyl groups with a compound having carboxyl groups and unsaturated bonds.

[0080] Examples of compounds having unsaturated bonds and glycidyl groups include glycidyl methacrylate.

[0081] Specific examples of compounds having a carboxyl group and an unsaturated bond include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, or alkyl maleic acid esters. Representative alkyl maleic acid esters include monomethyl maleic acid, ethyl maleic acid, n-propyl maleic acid, isopropyl maleic acid, n-butyl maleic acid, n-hexyl maleic acid, n-octyl maleic acid, 2-ethylhexyl maleic acid, n-nonyl maleic acid, or n-dodecyl maleic acid. The compounds exemplified above as having a carboxyl group and an unsaturated bond can be used individually or in combination of two or more.

[0082] Examples of compounds other than those having unsaturated bonds and glycidyl groups, used to manufacture copolymers of the above-mentioned compounds having unsaturated bonds and glycidyl groups, or copolymers of polymers obtained by further reacting compounds having carboxyl groups and unsaturated bonds, are listed below, but are not necessarily limited thereto.

[0083] The other compounds mentioned above may possess unsaturated bonds capable of copolymerizing with compounds having unsaturated bonds and glycidyl groups, or compounds having carboxyl groups and unsaturated bonds. Specific examples include: styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and other aromatic vinyl compounds; methyl (meth)acrylate, (methyl... Ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and other alkyl methacrylates; cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, 2-dicyclopentoxyethyl methacrylate, isobornyl methacrylate, and other alicyclic methacrylates; phenyl methacrylate, (methyl... (Meth)acrylate aryl esters such as benzyl acrylate; (Meth)acrylate hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methylphenylmaleimide N-substituted maleimide compounds such as oxyphenyl maleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide; 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.

[0084] The other compounds exemplified above can be used individually or in combination of two or more.

[0085] Preferably, the weight-average molecular weight of the alkali-soluble resin, converted from polystyrene, is in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. If the weight-average molecular weight of the alkali-soluble resin is less than 3,000 or greater than 100,000, there is a disadvantage that during development, it is impossible to prevent film reduction, which may lead to the peeling off of the patterned area, or poor development may result in residual film or residue.

[0086] The acid value of the above-mentioned alkali-soluble resin is 30 to 150 mg KOH / g, preferably 40 to 140 mg KOH / g, more preferably 50 to 120 mg KOH / g, and most preferably 50 to 100 mg KOH / g.

[0087] If the acid value of the above-mentioned alkali-soluble resin is 30 to 150 mg KOH / g, it can improve the solubility and film retention rate in the developer and form a high-resolution pattern, and is therefore preferred.

[0088] Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1g of acrylic polymer, and it can usually be determined by titration with an aqueous solution of potassium hydroxide.

[0089] The content of the alkali-soluble resin relative to the total weight of the photosensitive resin composition can be 5 to 80% by weight, preferably 15 to 65% by weight.

[0090] If the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient to easily form a pattern, and it can prevent the reduction of the film in the pixel part of the exposed part during development, thereby improving the peeling of the non-pixel part.

[0091] Thiol compounds containing ether bonds

[0092] The present invention comprises thiols (-SH) containing ether (-O-) bonds. The thiols containing ether bonds are not particularly limited as long as they contain ether bonds and thiols in the molecule, but are preferably characterized by specifically containing one or more compounds selected from those represented by the following chemical formulas 2 and 3.

[0093] [Chemical Formula 2]

[0094]

[0095] [Chemical Formula 3]

[0096]

[0097] In the above chemical formulas 2 and 3, R3 can each independently be a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are straight-chain or branched and have 1 to 10 carbon atoms that are terminally substituted with a thiol group (-SH), and R4 to R6 can each independently be hydrogen (H), a thiol group (-SH) or one or more alkyl groups with 1 to 10 carbon atoms that are terminally substituted with a thiol group (-SH).

[0098] More specifically, in one embodiment of the present invention, the above-mentioned thiol compound containing an ether bond may be represented by the following chemical formula 4 or chemical formula 5.

[0099] [Chemical Formula 4]

[0100]

[0101] In the above chemical formula 4, R7 can be an alkylene group with 1 to 10 carbon atoms, m1 and n1 can each be an integer from 1 to 3, and m1 + n1 = 4.

[0102] [Chemical Formula 5]

[0103]

[0104] In the above chemical formula 5, R8 can be an alkylene group with 1 to 10 carbon atoms, m2, m3, n2 and n3 can be integers from 1 to 3, and m2+n2=3, m3+n3=3.

[0105] Compounds such as pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and pentaerythritol tetra(3-mercaptobutyrate), which have been used as thiols in the past, all contain ester bonds in their molecular structure. These thiols containing ester bonds are highly reactive to solvent decomposition, thus significantly reducing their water and alkali resistance, and potentially leading to a decline in long-term storage stability and time-related stability. However, the photosensitive resin composition of the present invention, containing thiols with ether bonds, exhibits excellent water resistance, heat resistance, alkali resistance, and chemical resistance due to its high resistance to solvent decomposition. Furthermore, the photosensitive resin composition of the present invention exhibits excellent adhesion to the substrate due to the flexible framework of thiol compounds containing ether bonds. Even in low-temperature processes, it exhibits a high ratio of development speed, resulting in clear exposure and non-exposure areas due to excellent light-dark ratio. Moreover, it also exhibits excellent preservation stability when exposed to stripping solution in subsequent processes without surface damage, swelling, or film shrinkage.

[0106] The photosensitive resin composition of the present invention has the advantage of being able to form a low-dielectric organic insulating film with low dielectric properties and capable of low-temperature curing by simultaneously comprising an alkali-soluble resin polymerized from the compound represented by the above-described chemical formula 1 and a thiol compound containing an ether bond selected from the compounds represented by the above-described chemical formulas 2 and 3.

[0107] Relative to the total weight of the photosensitive resin composition, the content of the thiol compound containing ether bonds in this invention can be from 0.5 to 25% by weight, preferably from 1 to 9% by weight, and more preferably from 1 to 6% by weight. If the content is lower than the above content, swelling and film shrinkage may occur when exposed to the stripping solution in subsequent processes. If the content is higher than the above content, the unexposed areas may not dissolve in the developer, resulting in residue, and resolution may be reduced.

[0108] Photopolymerizable unsaturated monomers

[0109] In this invention, the photopolymerizable unsaturated monomer is a compound that can be polymerized by the action of a photopolymerization initiator described later. As a component that increases the crosslinking density and enhances the mechanical properties of the pattern, photopolymerizable unsaturated monomers used in the art can be used without particular limitation.

[0110] As one example, the aforementioned photopolymerizable unsaturated monomers may include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

[0111] Specific examples of the aforementioned monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

[0112] Specific examples of the aforementioned 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, and 3-methylpentyl glycol di(meth)acrylate.

[0113] Specific examples of other multifunctional monomers mentioned above include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0114] The content of the above-mentioned photopolymerizable unsaturated monomer can be 5 to 90% by weight relative to the total weight of the composition, preferably 5 to 50% by weight. When the content is within the above range, the durability of the pattern and the developability of the composition can be improved.

[0115] The above-mentioned alkali-soluble resin and the above-mentioned photopolymerizable unsaturated monomer may be contained in a weight ratio of 1:0.2 to 2. In this case, it can have the advantages of exhibiting excellent pattern shape in the exposure section and exhibiting excellent film reduction rate.

[0116] Photopolymerization initiator

[0117] The aforementioned photopolymerization initiators serve to initiate free radical reactions in the photosensitive resin composition, thereby causing curing and increasing sensitivity. This invention is not particularly limited; any compound that generates free radicals that can be exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays can be used without restriction. Representative photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, biimidazole-based compounds, triazine-based compounds, oxime ester-based compounds, and thioxanone-based compounds. In this invention, the photopolymerization initiator can be used alone or in combination of two or more; preferably, one or more oxime ester-based compounds are used.

[0118] Examples of the aforementioned acetophenone compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoyladium dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one.

[0119] Examples of the aforementioned benzophenone compounds include benzophenone, 2,2'-hydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0120] Examples of the aforementioned biimidazole compounds include, for instance, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Phenylacetyl-1,2'-Biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 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.

[0121] Examples of the aforementioned triazine compounds include, for instance, 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, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethylene]. [ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0122] Examples of the aforementioned oxime ester compounds include, for example, o-ethoxycarbonyl-α-oximino-1-phenylpropane-1-one, 1,2-octanedione-1-(4-phenylthio)phenyl-2-(o-benzoyl oxime), acetone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(o-acetyl oxime), and commercially available products include CGI-124 (Ciba Specialty Chemicals), CGI-224 (Ciba Specialty Chemicals), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adico), and NCI-831 (Adico).

[0123] Examples of the aforementioned thioxanthone compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0124] In addition, there are also bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc., which are commercially available products, such as Irgacure 819 (BASF).

[0125] The aforementioned photopolymerization initiator can be used in conjunction with a photopolymerization initiation aid. The aforementioned photopolymerization initiation aid can be used to promote the polymerization of photocurable compounds initiated by the photopolymerization initiator.

[0126] Examples of photopolymerization initiators include amine compounds and alkoxyanthracene compounds. Specific examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as michalcone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and 4,4'-bis(N,N'-dimethylamino)-benzophenone, among which 4,4'-bis(N,N'-dimethylamino)-benzophenone is preferred.

[0127] Specific examples of the aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photopolymerization initiators can be used individually or in combination of two or more. Furthermore, commercially available products such as EAB-F (trade name, manufactured by Hodogaya Chemical Co., Ltd.) can also be used as photopolymerization initiators.

[0128] Specific examples of preferred combinations of the aforementioned photopolymerization initiators and photopolymerization initiation aids include: diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropane-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenyl one and 4,4'-bis(diethylamino)benzophenone. Oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one and 4,4'-bis(diethylamino)benzophenone; combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one and 4,4'-bis(diethylamino)benzophenone, etc., preferably combinations of 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one and 4,4'-bis(diethylamino)benzophenone, combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one and 4,4'-bis(N,N'-dimethylamino)benzophenone, etc.

[0129] When both the above-described photopolymerization initiator and photopolymerization initiation aid are used, the content of the photopolymerization initiation aid is preferably 0.01 to 5 mol relative to 1 mol of the photopolymerization initiator. When the content of the photopolymerization initiation aid is within the above-described range, the sensitivity of the photosensitive resin composition is further improved, and the productivity of the cured film formed using this composition is increased; therefore, this is preferred.

[0130] The content of the photopolymerization initiator relative to the total weight of the photosensitive resin composition can be from 0.1 to 10% by weight, preferably from 0.5 to 7% by weight. If the content is within this range, it is preferable from the perspectives of increasing the sensitivity of the photosensitive resin composition, shortening the exposure time, easily adjusting pattern formation, and improving curing degree and straightness. If the content is greater than 10% by weight, the linewidth increases excessively, making it impossible to maintain high resolution.

[0131] solvent

[0132] In this invention, the solvent can be any solvent commonly used in photosensitive resin compositions, as long as it is effective in dissolving the other components contained in the photosensitive resin composition of this invention. Ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferred.

[0133] Specific examples of the solvents mentioned above include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and other ethylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. Alkylene glycol alkyl ether acetates such as monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

[0134] From the perspective of coatability and drying properties, the solvents mentioned above are preferably organic solvents with a boiling point of 100°C to 200°C, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc.

[0135] The solvents mentioned above can be used individually or in combination.

[0136] The solvent content can be a margin that makes the total weight of the photosensitive resin composition 100% by weight. Specifically, in this invention, "margin" means a margin that makes the total weight of the composition containing the essential components of this invention and other additional components 100% by weight, and does not limit the composition of this invention to not containing additional components due to the meaning of "margin". For example, relative to the total weight of the photosensitive resin composition of this invention, it can be 10 to 90% by weight, preferably 20 to 75% by weight. When the solvent is included within the above range, it provides the effect of improved coatability when coating with coating apparatus such as roller coaters, spin coaters, slot coaters, slot applicators (sometimes also called die coaters), and spray coaters.

[0137] Other additives

[0138] In addition to the aforementioned components, the photosensitive resin composition of the present invention may also include additives, to enhance the coatability, adhesion, etc., of the cured film, as needed by those skilled in the art, without prejudice to the purpose of the present invention. For this purpose, it may further include components commonly used in the art, such as other polymeric compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and / or anti-gelling agents, etc., and may also include additives commonly used in the art to which this invention pertains. These may be used alone or in combination or in any ratio.

[0139] Specific examples of the other polymer compounds mentioned above include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and other thermoplastic resins.

[0140] The aforementioned curing agents are used to improve deep curing and mechanical strength. Specific examples of curing agents include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0141] Specific examples of epoxy compounds in the aforementioned curing agents include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenolic varnish type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, (meth)acrylate glycidyl ester (co)polymers, triglycidyl isocyanurate, etc.

[0142] Specific examples of oxobutane compounds in the aforementioned curing agents include carbonate oxobutane, xylene oxobutane, adipate bisoxetane, terephthalate oxobutane, and cyclohexanedicarboxylic acid oxobutane.

[0143] The aforementioned curing agent can be used in conjunction with a curing aid compound, which, together with the curing agent, enables the ring-opening polymerization of the epoxy groups of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of such curing aid compounds include polycarboxylic acids, polycarboxylic anhydrides, and acid-generating agents. Commercially available epoxy resin curing agents can be used as polycarboxylic anhydrides. Specific examples of such epoxy resin curing agents include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Industries, Ltd.), RIKACID HH (trade name, manufactured by Shin Nippon Rikka Co., Ltd.), and MH-700 (trade name, manufactured by Shin Nippon Rikka Co., Ltd.). The curing agents exemplified above can be used alone or in combination of two or more.

[0144] The aforementioned surfactants can be used to further improve the film-forming properties of the photosensitive resin composition, and can be added as silane coupling agents or leveling agents to enhance coatability and adhesion. Examples include silicone-based, fluorinated, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, which can be used individually or in combination of two or more. Silicone-based and / or fluorinated surfactants are preferred, but not limited thereto.

[0145] The aforementioned silicone surfactants include, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicones, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicones.

[0146] The aforementioned fluorinated surfactants include, for example, commercially available products such as MEGAFACE F-470, F-471, F-475, F-482, F-489, and F-554 from Dai Nippon Ink Chemical Industry Co., Ltd. The surfactants exemplified above can be used individually or in combination of two or more.

[0147] Specific examples of the aforementioned adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltrimethoxysilane, and 3-isocyanate-propyltriethoxysilane. The adhesion promoters described above can be used individually or in combination of two or more.

[0148] The content of the above-mentioned adhesion promoter, relative to 100 parts by weight of the solid components of the photosensitive resin composition, is typically 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight.

[0149] Specific examples of the aforementioned antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

[0150] Specific examples of the aforementioned ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0151] Specific examples of the aforementioned anti-condensing agents include sodium polyacrylate.

[0152] The above-mentioned additives may be added as appropriate by those skilled in the art without impairing the effects of the present invention. For example, the above-mentioned additives may be used at 0.05 to 10% by weight, preferably 0.1 to 9% by weight, and more preferably 0.1 to 8% by weight, relative to the total weight of the photosensitive resin composition, but are not limited thereto.

[0153] <Patterns made from photosensitive resin compositions>

[0154] The present invention includes patterns manufactured from cured products of the above-described photosensitive resin compositions.

[0155] The pattern made from the above-mentioned photosensitive resin composition is characterized by a value of 3.25 or less after curing, as calculated by the following formula 1.

[0156] [Mathematical Expression 1]

[0157] k = (C × A) / (εo × d)

[0158] In the above mathematical formula 1, k represents the dielectric ratio, C represents the capacitance, εo represents the vacuum dielectric constant, d represents the thickness of the thin film, and A represents the contact cross-sectional area of ​​the electrode.

[0159] The dielectric constant is preferably 3.25 or less, and most preferably 3.00 or less, which is preferred from the perspective of manufacturing large-area organic insulating films.

[0160] The pattern of the present invention is characterized by its ability to cure at temperatures below 100°C. Besides being formed from the aforementioned photosensitive resin composition, the pattern of the present invention can be manufactured using methods known in the art. In the present invention, the curing temperature can be based on pre-baking and / or post-baking temperatures.

[0161] When forming a photocurable pattern, the aforementioned photosensitive resin composition can be coated onto a substrate and then exposed and developed to form the pattern. Pre-baking or post-baking processes can be performed between these steps. The heating temperature and time for pre-baking are selected based on the solvent used; for example, it is performed at a temperature of 80°C to 100°C for 1 to 3 minutes. The exposure is performed using an exposure machine and through a photomask, thereby exposing only the portion corresponding to the pattern. The irradiated light can be, for example, visible light, ultraviolet light, X-rays, and electron beams. The exposure time is not particularly limited and can be appropriately varied depending on the exposure apparatus, the wavelength of the irradiated light, or the exposure intensity. However, a preferred exposure time can be varied within the range of 5 to 250 seconds. Then, as a step aimed at increasing hardness to improve the adhesion between the patterned film and the substrate, a heat treatment can be performed at a curing temperature, preferably 80 to 100°C, for 10 to 120 minutes to complete the curing process. This heat treatment can be performed using an oven or a heating plate, but is not limited to these methods.

[0162] The aforementioned pattern can be a photocurable pattern selected from the group consisting of array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored resist pattern, pattern containing scatterers, and pattern containing quantum dots.

[0163] The photocurable pattern of the present invention can utilize thiol compounds containing ether structures to prevent free radical oxygen from being affected by oxygen inhibition during the exposure process, thereby forming a coating film exhibiting excellent development retention rate. Furthermore, it inhibits solvent decomposition when exposed to stripping solution in subsequent processes, thus having the advantages of preventing swelling or shrinkage of the coating film and reduced adhesion.

[0164] <Display Device>

[0165] This invention provides a display device comprising a pattern manufactured from the aforementioned photosensitive resin composition. Examples of such display devices include, but are not limited to, liquid crystal displays (LCDs), organic EL displays (including organic EL displays, OLEDs, and QLEDs), flexible displays, liquid crystal projectors, display devices for game consoles, display devices for portable terminals such as mobile phones, display devices for digital cameras, and display devices for navigation devices. In addition to the aforementioned pattern, the display device may also include configurations commonly used in the art.

[0166] The following are experimental examples, including specific embodiments and comparative examples, to aid in understanding the present invention. However, these are merely illustrative examples and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments within the scope and technical concept of the present invention, and such changes and modifications also fall within the scope of the appended claims. In the examples, "%" and "parts" are "mass %" and "parts by mass" respectively, unless otherwise stated.

[0167] Synthesis Example 1: Synthesis of Alkali-Soluble Resin (A-1)

[0168] In the method for manufacturing the alkali-soluble resin (A-1) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C13MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-1. The alkali-soluble resin A-1 produced above was confirmed to have an acid value of 80 mg KOH / g and a weight-average molecular weight of 7,100 as determined by GPC.

[0169] Synthesis Example 2: Synthesis of Alkali-Soluble Resin (A-2)

[0170] In the method for manufacturing the alkali-soluble resin (A-2) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C16MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-2. The alkali-soluble resin A-2 produced above was confirmed to have an acid value of 72 mg KOH / g and a weight-average molecular weight of 6,800 as determined by GPC.

[0171] Synthesis Example 3: Synthesis of Alkali-Soluble Resin (A-3)

[0172] In the method for manufacturing the alkali-soluble resin (A-3) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as a reaction vessel. C16MA / o-phenylphenoxyethyl acrylate (CAS No. 72009-86-0) / methacrylic acid is added together with a reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-3. The alkali-soluble resin A-3 produced above was confirmed to have an acid value of 71 mg KOH / g and a weight-average molecular weight of 8,200 as determined by GPC.

[0173] Synthesis Example 4: Synthesis of Alkali-Soluble Resin (A-4)

[0174] In the method for manufacturing the alkali-soluble resin (A-4) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C18MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-4. The alkali-soluble resin A-4 produced above was confirmed to have an acid value of 77 mg KOH / g and a weight-average molecular weight of 6,500 as determined by GPC.

[0175] Synthesis Example 5: Synthesis of Alkali-Soluble Resin (A-5)

[0176] In the method for manufacturing the alkali-soluble resin (A-5) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as a reaction vessel. C18MA / o-phenylphenoxyethyl acrylate (CAS No. 72009-86-0) / methacrylic acid is added together with a reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-5. The alkali-soluble resin A-5 produced above was confirmed to have an acid value of 77 mg KOH / g and a weight-average molecular weight of 5,200 as determined by GPC.

[0177] Synthesis Example 6: Synthesis of Alkali-Soluble Resin (A-6)

[0178] In the method for manufacturing the alkali-soluble resin (A-6) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C12MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-6. The alkali-soluble resin A-6 produced above was confirmed to have an acid value of 74 mg KOH / g and a weight-average molecular weight of 7,100 as determined by GPC.

[0179] Synthesis Example 7: Synthesis of Comparative Alkali-Soluble Resin (A-7)

[0180] In the method for manufacturing the alkali-soluble resin (A-7) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C10MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-7. The alkali-soluble resin A-7 produced above was confirmed to have an acid value of 74 mg KOH / g and a weight-average molecular weight of 6,800 as determined by GPC.

[0181] Synthesis Example 8: Synthesis of Comparative Alkali-Soluble Resin (A-8)

[0182] In the method for manufacturing the alkali-soluble resin (A-8) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. 2-hydroxyethyl methacrylate / vinyl toluene / methacrylic acid is added to the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-8. The alkali-soluble resin A-8 produced above was confirmed to have an acid value of 80 mg KOH / g and a weight-average molecular weight of 6,650 as determined by GPC.

[0183] Synthesis Example 9: Synthesis of Comparative Alkali-Soluble Resin (A-9)

[0184] In the method for manufacturing the alkali-soluble resin (A-9) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as the reaction vessel. C24MA / vinyl toluene / methacrylic acid is added together with the reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the reaction is carried out dropwise over 2 hours, thereby producing the alkali-soluble resin A-9. The alkali-soluble resin A-9 produced above was confirmed to have an acid value of 73 mg KOH / g and a weight-average molecular weight of 5,200 as determined by GPC.

[0185] Synthesis Example 10: Synthesis of Comparative Alkali-Soluble Resin (A-10)

[0186] In the method for manufacturing the alkali-soluble resin (A-10) of the present invention, a three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer is used as a reaction vessel. C10MA / o-phenylphenoxyethyl acrylate (CAS No. 72009-86-0) / methacrylic acid is added together with a reaction solvent (propylene glycol monomethyl ether acetate, PGMEA) at a molar ratio of 52.4 / 10 / 37.6. The mixture is then heated to 110°C under a nitrogen atmosphere and stirred for 30 minutes. Then, 17.6 moles of glycidyl methacrylate and the polymerization initiator 2,2'-azobisisobutyronitrile (AIBN) are dissolved in the reaction solvent, and the mixture is reacted dropwise over 2 hours to produce the alkali-soluble resin A-10. The alkali-soluble resin A-10 produced above was confirmed to have an acid value of 66 mg KOH / g and a weight-average molecular weight of 6,610 as determined by GPC.

[0187] Synthetic Example 11: Synthesis of Pentaerythritol tripropanethiol (X-1)

[0188] In a round-bottom flask, pentaerythritol triallyl ether (1.37 mol) was added and heated to 40 °C. Thioacetic acid (4.51 mol) was added dropwise at a molar ratio of 1:3.3 to pentaerythritol triallyl ether, and the mixture was stirred at 40 °C for 4 hours. A 20% ammonia solution (560 g) was added to the reactants, and the reaction was carried out at 55 °C for 15 hours. After separating the organic layer, the mixture was washed with toluene (490 g) and a 5% sulfuric acid solution (350 g), and the organic layer was separated and extracted. Water (350 g) was then added to the organic layer. The organic layer was separated, concentrated, and dried to obtain pentaerythritol tripropanethiol (478 g, 98% yield) as a colorless and transparent oil (referred to as PEPT).

[0189] The NMR analysis results are as follows.

[0190] 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)

[0191] Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions

[0192] The photosensitive resin compositions of the examples and comparative examples were manufactured with reference to the compositions and weights described in Tables 1 and 2 below.

[0193] Specifically, as the thiol compound (X) containing an ether bond, X-1 manufactured in the above-described synthesis example 11 or X-2, a commercially available product, was used respectively; as the alkali-soluble resin (A), A-1 to A-10 manufactured in the above-described synthesis examples 1 to 10 were used respectively.

[0194] [Table 1]

[0195]

[0196] [Table 2]

[0197]

[0198] 1) The alkali-soluble resin prepared according to Synthesis Example 1;

[0199] 2) The alkali-soluble resin prepared according to Synthesis Example 2;

[0200] 3) The alkali-soluble resin prepared according to Synthesis Example 3;

[0201] 4) The alkali-soluble resin prepared according to Synthesis Example 4;

[0202] 5) The alkali-soluble resin prepared according to Synthesis Example 5;

[0203] 6) The alkali-soluble resin prepared according to Synthesis Example 6;

[0204] 7) The alkali-soluble resin prepared according to Synthesis Example 7;

[0205] 8) The alkali-soluble resin prepared according to Synthesis Example 8;

[0206] 9) The alkali-soluble resin prepared according to Synthesis Example 9;

[0207] 10) An alkali-soluble resin prepared according to Synthesis Example 10;

[0208] 11) Dipentaerythritol hexaacrylate (KAYARAD DPHA): Manufactured by Nippon Kayaku;

[0209] 12) Irgacure 819: Manufactured by BASF;

[0210] 13) Irgacure OXE-01: Manufactured by BASF;

[0211] 14) The thiol compound (chemical formula 2) prepared according to Synthesis Example 11;

[0212] 15) Trimethylolpropane tris(3-mercaptopropionate): manufactured by SC Organic Chemistry;

[0213] 16) Propylene glycol monomethyl ether acetate: manufactured by Sigma-Aldrich.

[0214] Experimental Example: Evaluation of the Physical Properties of Patterns

[0215] A 5×5cm glass substrate (Eagle 2000; manufactured by Corning) was sequentially cleaned with neutral detergent, water, and ethanol, and then dried. The photosensitive resin compositions prepared in the above examples and comparative examples were spin-coated onto the glass substrates, and then pre-baked at 85°C for 120 seconds using a hot plate. After the pre-baked substrates were cooled to room temperature, a 50μm gap was set between them and a quartz glass photomask, and an exposure machine (MPA-600FA; manufactured by Canon) was used at 30mJ / cm². 2 The exposure amount (365nm reference) of the irradiated light.

[0216] At this point, a photomask is used, in which square patterns (hole patterns) of 5-20 μm are formed on the same plane, spaced 100 μm apart. After light irradiation, the image is developed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, washed with ultrapure water, and then dried under nitrogen, thereby forming a pattern on the aforementioned photosensitive resin composition film. The image is then post-baked at 85°C for 2 hours in an oven.

[0217] The physical properties of the above pattern were evaluated as follows (1) to (5), and the results are shown in Table 3 below.

[0218] (1) Evaluation of dielectric constant

[0219] The photocurable ink compositions prepared in the examples and comparative examples were coated onto a boron-doped P-type silicon wafer to a thickness of 8 μm after curing. After exposure to a UV LED at 395 nm, a circular aluminum film with a diameter of 1 mm was deposited at a thickness of 2000 Å using a hard mask with a diameter of 1 mm. This completed the dielectric constant measurement of the metal-insulator-metal (MIM) structure. For such films, the capacitance was measured at approximately 100 kHz using a precision LCR meter (PRECISION LCR METER, HP4284A) equipped with a probe station (Micromanipulatior 6200 probe station). After measuring the film thickness using an ellipsometer, the dielectric constant was calculated using the following mathematical formula 1.

[0220] [Mathematical Expression 1]

[0221] k = (C × A) / (εo × d)

[0222] In the above formula, k represents the dielectric ratio, C represents the capacitance, εo represents the vacuum dielectric constant, d represents the thickness of the thin film, and A represents the contact cross-sectional area of ​​the electrode.

[0223] (2) Evaluation of chemical resistance (sealing)

[0224] After immersing the above patterns in NMP aqueous solution for 6 minutes, the minimum width of the line and gap mask patterns after sealing was evaluated.

[0225] <Evaluation Criteria>

[0226] 5: The minimum width of the mask for the dense line pattern is 5μm;

[0227] 7: The minimum width of the mask for the dense line pattern is 7μm;

[0228] 10: The minimum width of the mask for the dense line pattern is 10 μm;

[0229] 20: The minimum width of the mask for the dense line pattern is 20 μm;

[0230] ×: Peeling has occurred.

[0231] (3) Evaluation of chemical resistance (film thickness change)

[0232] The thickness change of the above pattern was measured before and after immersion in NMP aqueous solution for 6 minutes.

[0233] (4) Residue Evaluation

[0234] An optical microscope was used to evaluate whether there were any residues in the hole pattern.

[0235] <Evaluation Criteria>

[0236] No residue: ○;

[0237] There are residues: ×.

[0238] (5) Refractive index measurement

[0239] Except for the absence of a mask, exposure was performed in the same manner as the pattern fabrication method described above. For the cured film thus formed, linear polarization was measured using an ellipsometer (JA Woollam Co., M-2000) at 25°C and 50%RH with incident angles of 65°, 70°, and 75°, respectively, within a wavelength range of 200 nm to 1000 nm. The measured linear polarization data (ellipsometer data (Ψ, Δ)) were optimized (fitted) using the Cauchy model from Equation 2 below with an MSE of 70 or less using Complete EASE software, thereby calculating the refractive index at a wavelength of 550 nm.

[0240] [Mathematical Expression 2]

[0241]

[0242] In the above mathematical formula 2, n(λ) is the refractive index at wavelength λ, λ is in the range of 300nm to 1800nm, and A, B and C are Cauchy parameters.

[0243] [Table 3]

[0244]

[0245] As shown in Table 3 above, experiments have confirmed that patterns manufactured using the photosensitive resin compositions of Examples 1 to 8 of the present invention exhibit a low dielectric constant of less than 3.25 and a low refractive index of 1.48 to 1.52 under low-temperature processing conditions below 100°C. They also exhibit excellent chemical resistance (resistance to reagents and solvents) and do not produce residues, thus demonstrating excellent reliability for metal processing.

Claims

1. A photosensitive resin composition, characterized in that, It comprises: an alkali-soluble resin polymerized from compounds represented by the following chemical formula 1; and a thiol compound containing an ether bond. The thiol compound containing an ether bond comprises one or more compounds selected from those represented by chemical formulas 2 and 3 below. Chemical Formula 1 In the chemical formula 1, R1 is hydrogen or methyl. R2 is an alkyl group having 12 to 21 carbon atoms or a cycloalkyl group having 12 to 21 carbon atoms. Chemical formula 2 Chemical formula 3 In chemical formulas 2 and 3, R3 is each independently a thiol group or one or more straight-chain or branched alkyl groups with 1 to 10 carbon atoms whose ends are replaced by thiol groups. R4 to R6 are each independently a straight-chain or branched alkyl group with 1 to 10 carbon atoms, consisting of hydrogen, a thiol group, or one or more thiol groups at the end.

2. The photosensitive resin composition according to claim 1, characterized in that, The compound represented by chemical formula 1 has a branched structure in its R2 component.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, R2 of the compound represented by chemical formula 1 is an alkyl group or a cycloalkyl group having 13 to 18 carbon atoms.

4. The photosensitive resin composition according to claim 1 or 2, characterized in that, The thiol compounds containing ether bonds are represented by the following chemical formula 4 or chemical formula 5. Chemical Formula 4 In the chemical formula 4, R7 is an alkylene group having 1 to 10 carbon atoms. m1 and n1 are each independent integers from 1 to 3, and m1 + n1 = 4. Chemical formula 5 In the chemical formula 5, R8 are each an alkylene group having 1 to 10 carbon atoms. m2, m3, n2, and n3 are each independent integers from 1 to 3, and m2 + n2 = 3, m3 + n3 = 3.

5. The photosensitive resin composition according to claim 1 or 2, characterized in that, It also contains one or more selected from photopolymerizable unsaturated monomers, photopolymerization initiators, and solvents.

6. The photosensitive resin composition according to claim 1 or 2, characterized in that, The pattern manufactured from the photosensitive resin composition, after curing, has a value of 3.25 or less as calculated by the following formula 1. Mathematical Formula 1 k = (C × A) / (εo × d) In the mathematical formula 1, k represents the dielectric constant, C represents the capacitance, εo represents the vacuum dielectric constant, d represents the thickness of the thin film, and A represents the contact cross-sectional area of ​​the electrode.

7. The photosensitive resin composition according to claim 1 or 2, characterized in that, The photosensitive resin composition cures at temperatures below 100°C.

8. A pattern comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 7.

9. The pattern according to claim 8, characterized in that, The pattern has a refractive index of 1.48 to 1.52 after curing.

10. The pattern according to claim 8, characterized in that, The pattern is selected from the group consisting of free array planarization film pattern, protective film pattern, insulating film pattern, photoresist pattern, black matrix pattern, columnar spacer pattern, black columnar spacer, colored resist pattern, pattern containing scatterer, and pattern containing quantum dots.

11. A display device comprising the pattern of claim 8.

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