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 being characterized by containing (A) a binder resin, (B) a photocurable compound, (C) an initiator, (D) an additive, and (E) a solvent, the binder resin (A) is obtained by polymerizing a compound containing tetrahydrofurfuryl methacrylate and a maleic anhydride structure, the weight-average molecular weight (Mw) of the binder resin (A) is 4000-15000, and the additive (D) contains a thiol compound having an ether bond. The present invention is manufactured from the photosensitive resin composition, and thus can provide a display device having excellent chemical resistance, excellent minimum resolution of a contact hole pattern of 5 [mu] m, low yellow index (Y.I.) value and improved resolution, and excellent reliability, wherein the generation of outgassing of the pattern is suppressed even under low-temperature curing conditions of 100 DEG C or less.

Description

Technical Field

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

[0002] In the field of displays, photosensitive resin compositions are used to form various cured patterns such as photoresists, insulating films, protective films, black matrices, and column spacers. Specifically, the photosensitive resin composition is selectively exposed and developed through a photolithography process to form a desired pattern. In this process, in order to improve the yield in the process and the physical properties of the application object, a photosensitive resin composition with high sensitivity is required.

[0003] Specifically, the pattern formation of the photosensitive resin composition utilizes photolithography, that is, the polarity change and crosslinking reaction of polymers occurring through a photoreaction. In particular, the above pattern formation utilizes the change characteristics of solubility in solvents such as an aqueous alkali solution after exposure.

[0004] A desired photocured pattern is formed by selectively exposing and developing the photosensitive resin composition through a photolithography process. In this process, in order to improve the yield in the process and the physical properties of the application object, a photosensitive resin composition having excellent chemical and physical properties is required.

[0005] In recent years, displays are used in a flexible form, and thus flexible displays capable of displaying in a flexible state without being damaged even when bent or rolled up are being developed. Therefore, the materials that can be used are also limited to flexible polymer materials, and the manufacturing process also needs to be carried out under milder low-temperature conditions.

[0006] Accordingly, the curing conditions of the photosensitive resin composition also begin to require low-temperature curing instead of the conventional high-temperature curing. However, the low-temperature curing conditions have problems such as a decrease in reactivity and a decrease in the durability of the formed pattern. In addition, not only does the heat resistance deteriorate, but especially due to exposure to solvents used in subsequent processes, there are difficulties such as swelling caused by surface penetration and a decrease in adhesion, poor chemical resistance characteristics, damage to the pattern surface, and a decrease in the adhesion to the underlying substrate.

[0007] In the case of Korean Patent Publication No. 10-2022-0168140, it can be confirmed that due to the use of a negative photosensitive resin composition, the resist film has alkali solubility, excellent reagent resistance, and high hardness. However, although a curable composition capable of low-temperature curing is desired, it does not start curing below 100 °C, so there are limitations in its use when forming a pattern on a flexible substrate containing a polymer or a substrate having an organic layer on the bottom.

[0008] Prior Art Documents

[0009] Patent Document

[0010] Patent Document 1: Korean Patent Publication No. 10-2022-0168140 Summary of the Invention

[0011] Problems to be Solved

[0012] The present invention aims to solve the problems in the above-mentioned prior art, and its purpose is to provide a photosensitive resin composition capable of manufacturing a pattern that exhibits excellent resolution and chemical resistance characteristics even under the conditions of a low-temperature curing process at 100 °C or lower, and in which out-gas generation is suppressed, a pattern formed therefrom, and a display device.

[0013] In addition, the present invention aims to solve the problems in the above-mentioned prior art, and its purpose is to provide a photosensitive resin composition capable of manufacturing a pattern that exhibits excellent characteristics such as excellent surface roughness, suppression of white turbidity, suppression of haze generation, flatness, adhesion, and surface uniformity even under the conditions of a low-temperature curing process at 100 °C or lower, a pattern formed therefrom, and a display device.

[0014] However, the problems to be solved in this application are not limited to the problems mentioned above, and those of ordinary skill in the art should be able to clearly understand other unmentioned problems based on the following description.

[0015] Means for Solving the Problems

[0016] To solve the above problems, the present invention provides a photosensitive resin composition, which is characterized by containing (A) a binder resin, (B) a photocurable compound, (C) an initiator, (D) an additive, and (E) a solvent, wherein the above-mentioned (A) binder resin is obtained by polymerization of a composition containing tetrahydrofurfuryl methacrylate and a compound having a maleic anhydride structure, the weight-average molecular weight (Mw) of the above-mentioned (A) binder resin is 4000 to 15000, and the above-mentioned (D) additive contains a thiol compound having an ether bond.

[0017] In the present invention, the compound having a maleic anhydride structure may further have a hydrocarbon ring structure having 3 to 20 carbon atoms.

[0018] In the present invention, the compound having a maleic anhydride structure may have a condensed bicyclic hydrocarbon ring structure having 6 to 16 carbon atoms.

[0019] In the present invention, the compound having a maleic anhydride structure may be one or more selected from methyl tetrahydro phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophtalic anhydride, and phthalic anhydride.

[0020] In the present invention, the double bond equivalent of the above-mentioned (A) binder resin may be 700 g / mol or less.

[0021] The weight average molecular weight (Mw) of the above-mentioned (A) binder resin may be 4,000 to 10,000.

[0022] The present invention is characterized in that the acid value of the above-mentioned (A) binder resin may be 20 mgKOH / g to 100 mgKOH / g.

[0023] In the present invention, in the total weight of the above composition, the weight ratio of the above-mentioned (A) binder resin:(B) photocurable compound may be 4:6 to 6:4.

[0024] The present invention is characterized in that the thiol compound having an ether bond may be represented by the following Chemical Formula 1 or Chemical Formula 2.

[0025] [Chemical Formula 1]

[0026]

[0027] [Chemical Formula 2]

[0028]

[0029] (In the above Chemical Formulas 1 to 2, R1 may be a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH), and R2 to R4 may each independently be hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH).)

[0030] The present invention is characterized in that the thiol compound having an ether bond may be represented by the following Chemical Formula 3 or Chemical Formula 4.

[0031] [Chemical Formula 3]

[0032]

[0033] (In the above Chemical Formula 3, R5 may be an alkylene group having 1 to 10 carbon atoms, and m1 and n1 may each independently be an integer of 1 to 3 and m1 + n1 = 4.)

[0034] [Chemical Formula 4]

[0035]

[0036] (In the above Chemical Formula 4, R6 may each independently be an alkylene group having 1 to 10 carbon atoms, and m2, m3, n2, and n3 may each independently be an integer of 1 to 3, and m2 + n2 = 3, m3 + n3 = 3.)

[0037] In the present invention, the above composition can be cured at a temperature below 100°C.

[0038] In addition, the present invention relates to a pattern including a cured product of the above photosensitive resin composition. The thickness of the pattern after curing can be 5 to 10 μm, and it can exhibit pore characteristics of 5 μm or less.

[0039] In addition, the film thickness of the halftone region of the above pattern can be 50% or more of the film thickness of the full-tone region.

[0040] In the present invention, the above pattern can be selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern including a scatterer, and a pattern including quantum dots.

[0041] In addition, the present invention relates to a display device including the above pattern.

[0042] Advantages of the Invention

[0043] Since the present invention is manufactured by including the above photosensitive resin composition, it is possible to provide a display device that suppresses outgassing of the pattern even under low-temperature curing conditions of 100°C or less, has excellent chemical resistance, has an excellent minimum resolution of 5 μm for a contact hole pattern, has a low yellow index (Y.I.) value and improved resolution, and has excellent reliability.

[0044] In addition, since the present invention is manufactured by including the above photosensitive resin composition, it is possible to provide a pattern that is uniform with a surface roughness of 3.0 nm or less even under low-temperature curing conditions of 100°C or less, suppresses the generation of cloudiness and / or haze, and has excellent physical properties such as flatness and adhesion. In particular, the above pattern is characterized in that the film thickness of the halftone region is 50% or more of the film thickness of the full-tone region, and thus it is possible to provide a display device with improved surface uniformity of the pattern and excellent reliability. Detailed implementation mode

[0045] The present invention relates to a photosensitive resin composition, a pattern formed therefrom, and a display device. The photosensitive resin composition is characterized by comprising (A) an adhesive resin, (B) a photocurable compound, (C) an initiator, (D) an additive, and (E) a solvent. The above (A) adhesive resin is obtained by polymerizing a composition containing tetrahydrofurfuryl methacrylate and a compound having a maleic anhydride structure. The weight average molecular weight (Mw) of the above (A) adhesive resin is 4,000 to 15,000. The above (D) additive contains a thiol compound having an ether bond. By using the above photosensitive resin composition in manufacturing, patterns with excellent optical properties such as resolution can be achieved even under low-temperature curing conditions of 100°C or lower, outgassing generation is suppressed, and physical properties such as chemical resistance are excellent, as well as a display device including the same. In addition, by using the photosensitive resin composition of the present invention in manufacturing, patterns with excellent surface roughness can be achieved even under low-temperature curing conditions of 100°C or lower, generation of cloudiness and / or haze is suppressed, and physical properties such as flatness and adhesion are excellent, as well as a display device including the same.

[0046] Hereinafter, the embodiments of the present invention will be described in more detail. However, the terms used in this specification are intended to describe the embodiments and are not intended to limit the present invention. In this specification, unless otherwise specified, the singular form also includes the plural form.

[0047] As used in this specification, "comprises" and / or "comprising" are used in a sense that does not exclude one or more other elements, steps, and / or components other than the recited elements, steps, and / or components.

[0048] <Photosensitive resin composition>

[0049] The photosensitive resin composition of the present invention may comprise (A) an adhesive resin, (B) a photocurable compound, (C) an initiator, (D) an additive, and (E) a solvent. As the above (D) additive, a thiol compound having an ether bond may be included, and other additives may also be included.

[0050] (A) Adhesive resin

[0051] The above-mentioned (A) binder resin contained in the photosensitive resin composition of the present invention is characterized in that it can be obtained by polymerizing tetrahydrofurfuryl methacrylate and a compound having a maleic anhydride structure, and the weight average molecular weight (Mw) of the above-mentioned (A) binder resin is 4,000 to 15,000.

[0052] The binder resin of the present invention can affect the patterning process of the photosensitive resin composition according to the molecular weight.

[0053] Considering from the aspects of improving the reactivity of the photosensitive resin composition under low-temperature conditions and improving chemical resistance, the weight average molecular weight of the above-mentioned binder resin (for example, measured by gel permeation chromatography (GPC) using polystyrene as a standard substance) can be 4,000 to 15,000, and preferably can be 4,000 to 10,000. If the above weight average molecular weight (Mw) range is satisfied, the CD deviation (CD-Bias) of the pattern can be achieved within an appropriate range to form a pattern with excellent resolution, and the chemical resistance of the pattern can also be improved. On the other hand, if the weight average molecular weight of the binder resin is higher than 15,000, the molecular weight becomes too large and the compatibility with other components of the photosensitive resin composition decreases, resulting in whitening of the coating film in the development step, the line width of the pattern may increase, leading to deterioration of the CD deviation characteristics, and the alkali solubility of the unexposed part may decrease, resulting in the problem of residue generation on the lower substrate. In addition, if the weight average molecular weight of the above-mentioned binder resin is lower than 4,000, reliability problems may occur.

[0054] Preferably, the compound having a maleic anhydride structure may further include a hydrocarbon ring structure having 3 to 20 carbon atoms, and more preferably may include a condensed bicyclic hydrocarbon ring structure having 6 to 16 carbon atoms. The above hydrocarbon ring structure is not limited to either a substituted or unsubstituted aromatic hydrocarbon and / or an alicyclic hydrocarbon. For example, the compounds having a maleic anhydride structure include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, chlorendic anhydride, etc. Among them, containing one or more selected from methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and phthalic anhydride is advantageous in terms of chemical resistance and reliability.

[0055] In one embodiment of the present invention, the double bond equivalent of the above (A) binder resin may be 700 g / mol or less.

[0056] The above double bond equivalent refers to the introduced amount of double bonds contained in the molecule defined by the following formula.

[0057] [Double bond equivalent] = [Molecular weight of the repeating structural unit] / [Number of double bonds in the repeating structural unit]

[0058] According to one embodiment of the present invention, if the double bond equivalent of the above (A) binder resin is 700 g / mol or less, advantages can be provided in terms of resolution and reliability formulation by adjusting photocuring. On the other hand, if the double bond equivalent exceeds the above range, it may affect the degree of photocuring, resulting in a decrease in resolution and may also cause deterioration of surface roughness. In the present invention, considering the above aspects, the double bond equivalent of the above binder resin is more preferably 680 g / mol or less.

[0059] In one embodiment of the present invention, the weight ratio of the above (A) binder resin: (B) photocurable compound is characterized by being 4:6 to 6:4. If the weight ratio satisfies the above range, it is possible to affect the surface roughness by adjusting the degree of curing during the polymerization process of the binder and the monomer, thereby providing an advantage during the subsequent process.

[0060] In addition, the binder resin contained in the photosensitive resin composition of the present invention is also a component that imparts solubility in the alkali developer used in the development process, and can be used without limitation as long as it can be dissolved in the alkali developer. The above binder resin is preferably produced by copolymerizing (b1) an ethylenically unsaturated monomer having a carboxyl group, so as to have solubility in the alkali developer used in the development treatment process when forming a pattern.

[0061] (b1) Ethylenically unsaturated monomer having a carboxyl group

[0062] Specific examples of the ethylenically 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; acid anhydrides of the above dicarboxylic acids; mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono(meth)acrylate, etc., and acrylic acid and methacrylic acid are preferred.

[0063] In addition, the above binder resin can be produced by polymerizing the ethylenically unsaturated monomer having a carboxyl group and (b2) a copolymerizable unsaturated monomer.

[0064] (b2) Copolymerizable unsaturated monomer

[0065] Specific examples of the copolymerizable unsaturated monomers include: glycidyl methacrylate as an unsaturated monomer having a glycidyl group; (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl ester, N-hydroxyethylacrylamide, etc., (meth)acrylic acid hydroxyethyl ester-based compounds such as vinylic unsaturated monomers having a hydroxyl group; styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc., aromatic vinyl compounds; 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-methoxyphenylmaleimide, etc., N-substituted maleimide-based compounds; (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid sec-butyl ester, (meth)acrylic acid tert-butyl ester, etc., (meth)acrylic acid alkyl ester-based compounds; (meth)acrylic acid cyclopentyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid 2-methylcyclohexyl ester, (meth)acrylic acid tricyclo[5.2.1.0 2,6]dec-8-yl ester, (meth)acrylic acid 2-dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyl ester, etc., alicyclic (meth)acrylic acid ester-based compounds; (meth)acrylic acid phenyl ester, (meth)acrylic acid benzyl ester, etc., (meth)acrylic acid aryl ester-based compounds; 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, etc., unsaturated oxetane compounds; etc., but not limited thereto. Each of the above copolymerizable unsaturated monomers can be used alone or in combination of two or more.

[0066] The binder resin of the present invention can affect the patterning process of the photosensitive resin composition according to the acid value and molecular weight. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can generally be determined by titration with an aqueous potassium hydroxide solution, which can affect the pattern formation during the process. The acid value of the above binder resin is preferably 20 to 100 mgKOH / g. If the acid value is within the above range, the solubility in the developer is improved, making it easier to dissolve the non-exposed part, and the sensitivity is increased. As a result, the pattern of the exposed part remains during development, improving the film remaining ratio, so it is preferred.

[0067] Considering the aspects of improving the reactivity of the photosensitive resin composition under low-temperature conditions and improving chemical resistance, the weight-average molecular weight of the above binder resin (for example, measured by gel permeation chromatography (GPC) using polystyrene as a standard substance) can be 4000 to 15000, and preferably can be 4000 to 10000. If the weight-average molecular weight (Mw) is within the above range, the CD deviation (CD-Bias) of the pattern can be achieved within an appropriate range to form a pattern with excellent resolution, and the chemical resistance of the pattern can also be improved. On the other hand, if the weight-average molecular weight of the binder resin is higher than 15000, the molecular weight becomes too large, reducing the compatibility with other components of the photosensitive resin composition, which may cause whitening of the coating film during the development step, the line width of the pattern may increase, resulting in deterioration of the CD deviation characteristics, and the alkali solubility of the unexposed part may decrease, causing problems such as residue generation on the lower substrate.

[0068] Relative to the total weight of the photosensitive resin composition, the content of the binder resin of the present invention can be 1 to 50% by weight, and preferably can be 5 to 30% by weight. If the content of the binder resin is within the above range, it is preferred in terms of ensuring high resolution and reliability. If the content is too low and below the above range, the degree of curing may be affected. If the content is too high and above the above range, the resolution may be reduced.

[0069] (B) Photocurable compound

[0070] The above (B) photocurable compound is a substance that polymerizes and cures upon irradiation with light such as ultraviolet light, which can increase the crosslinking density during the manufacturing process and enhance the mechanical properties of the photocured pattern. The above (B) photocurable compound is a compound that can be polymerized by the action of the following (C) initiator, which can impart excellent flatness and coatability to the cured film of the photosensitive resin composition of the present invention. Monofunctional monomers, difunctional monomers, or polyfunctional monomers can be used, and preferably polyfunctional monomers with two or more functional groups can be used.

[0071] Specific examples of the above-mentioned monofunctional monomers include, but are not limited to, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.

[0072] Specific examples of the above-mentioned difunctional monomers include, but are not limited to, 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.

[0073] Specific examples of the above-mentioned polyfunctional monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other monomers or oligomers.

[0074] With respect to the total weight of the photosensitive resin composition, the content of the photocurable compound of the present invention can be 2 to 25% by weight, preferably 3 to 20% by weight. If the content of the photocurable compound is within the above range, pattern properties can be formed well, excellent hardness and durability can be obtained, and the developability of the composition can be improved.

[0075] (C) Initiator

[0076] The above-mentioned (C) initiator plays a role in initiating the radical reaction of the photosensitive resin composition to cause curing and improving sensitivity. In the present invention, there is no particular limitation as long as it is a compound that generates radicals capable of initiating the polymerization of the above-mentioned (B) photocurable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron rays, X-rays, etc. Representative examples of the above-mentioned initiator include acetophenone-based compounds, benzophenone-based compounds, benzimidazole-based compounds, triazine-based compounds, oxime ester-based compounds, thioxanthone-based compounds, etc. In the present invention, the initiator can be used alone or in combination of two or more, and preferably one or more oxime ester-based compounds are used.

[0077] As the above-mentioned acetophenone-based compounds, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. can be cited.

[0078] As the above-mentioned benzophenone-based compounds, for example, benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. can be cited.

[0079] As the above-mentioned biimidazole-based compounds, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 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. can be cited.

[0080] As the above-mentioned triazine compounds, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethylidene]-1,3,5-triazine and the like can be cited.

[0081] As the above-mentioned oxime ester compounds, for example, it includes o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione-1-(4-phenylthio)phenyl-2-(o-benzoyl oxime), acetophenone-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-1-(o-acetyl oxime) and the like. As commercially available products, CGI-124 (Ciba-Geigy), CGI-224 (Ciba-Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (ADEKA), NCI-831 (ADEKA) and the like can be cited.

[0082] As the above-mentioned thioxanthone compounds, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be cited.

[0083] The above initiator can be used in combination with a photopolymerization initiator aid. The above photopolymerization initiator aid can be used to promote the polymerization of a photocurable compound polymerized by the initiator.

[0084] As the above-mentioned photo-polymerization initiation aid, amine compounds, alkoxy anthracene compounds, etc. can be cited. As specific examples of the above-mentioned amine compounds, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, 4,4'-bis(N,N'-dimethylamino)benzophenone, etc. can be cited. Among them, 4,4'-bis(N,N'-dimethylamino)benzophenone is preferred.

[0085] As specific examples of the above-mentioned alkoxy anthracene compounds, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. can be cited. Each of the above-mentioned photo-polymerization initiation aids can be used alone or in combination of two or more. In addition, as commercially available products, EAB-F (trade name, manufactured by Hodogaya Chemical Co., Ltd.) etc. can also be used as the above-mentioned photo-polymerization initiation aid.

[0086] As specific examples of the preferred combinations of the above-mentioned initiator and photo-polymerization initiation aid, the combination of diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; the combination of 2-methyl-2-morpholino-1-(4-methylphenylthio)propan-1-one and 4,4'-bis(diethylamino)benzophenone; the combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; the combination of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; the combination of 1-hydroxycyclohexyl phenyl ketone and 4,4'-bis(diethylamino)benzophenone; the combination of the oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; the combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone, etc. can be cited. Preferably, the combination of 2-methyl-2-morpholino-1-(4-methylphenylthio)propan-1-one and 4,4'-bis(diethylamino)benzophenone, the combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(N,N'-dimethylamino)benzophenone, etc. can be cited.

[0087] When the above initiator and the photo-polymerization initiator aid are used simultaneously, the content of the photo-polymerization initiator aid is preferably 0.01 to 5 moles relative to 1 mole of the above initiator. If the content of the photo-polymerization initiator aid is within the above content range, the sensitivity of the photosensitive resin composition is further improved, and the productivity of the cured film formed using the composition is also improved, so it is preferred.

[0088] Relative to the total weight of the photosensitive resin composition, the content of the above initiator can be 0.1 to 10% by weight, preferably 1 to 7% by weight. If the content is within the above range, the photosensitive resin composition will be highly sensitized to shorten the exposure time, the pattern formation is easily adjusted, and it is preferred in terms of improving the degree of curing and straightness. If the content is higher than 10% by weight, the line width will be over-expanded and high resolution cannot be maintained.

[0089] (D) Additive: Thiol compound having an ether bond

[0090] The (D) additive of the present invention contains a thiol compound having an ether bond. Specifically, the above thiol compound having an ether bond of the present invention can be represented by the following Chemical Formula 1 or Chemical Formula 2.

[0091] [Chemical Formula 1]

[0092]

[0093] [Chemical Formula 2]

[0094]

[0095] In the above Chemical Formulas 1 to 2, R1 to R4 may each independently be hydrogen or an alkyl group, and at least one or more may have a thiol group (-SH).

[0096] Preferably, R1 is a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH), more preferably a linear or branched alkyl group having 1 to 10 carbon atoms with a thiol group (-SH) at the end.

[0097] Preferably, R2 to R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups (-SH), more preferably each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms with a thiol group (-SH) at the end.

[0098] The alkylene group used in this specification refers to a linear or branched divalent hydrocarbon group composed of 1 to 20 carbon atoms. For example, it includes methylene, ethylene, n-propylene, isopropyl, etc., but is not limited thereto.

[0099] In addition, in one embodiment of the present invention, the photosensitive resin composition of the present invention may contain a thiol compound represented by the following Chemical Formula 3 or Chemical Formula 4.

[0100] [Chemical Formula 3]

[0101]

[0102] In the above Chemical Formula 3, each R5 may independently be an alkylene group having 1 to 10 carbon atoms, m1 and n1 may be integers of 1 to 3, and m1 + n1 = 4.

[0103] [Chemical Formula 4]

[0104]

[0105] In the above Chemical Formula 4, each R6 may independently be an alkylene group having 1 to 10 carbon atoms, m2, m3, n2 and n3 may each independently be an integer of 1 to 3, and m2 + n2 = 3, m3 + n3 = 3.

[0106] Conventionally, compounds such as pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and pentaerythritol tetra(3-mercaptobutyrate) used as thiol compounds all contain ester bonds within their molecular structures. Since such thiol compounds containing ester bonds have high reactivity to solvent decomposition, the effects such as water resistance and alkali resistance are significantly reduced, and problems may occur such as poor long-term storage stability and stability over time. However, the photosensitive resin composition containing the thiol compound having an ether bond of the present invention has high solvent decomposition resistance, and thus can have excellent properties such as water resistance, heat resistance, alkali resistance, and chemical resistance. In addition, due to the flexible skeleton of the thiol compound having an ether bond in the photosensitive resin composition of the present invention, excellent adhesion to the substrate can be exhibited, and even in a low-temperature process, due to excellent contrast, the development speed ratio is such that the exposed portion and the unexposed portion are clear, and no surface damage, swelling, or film shrinkage occurs when exposed to the stripping solution in the subsequent process, and excellent storage stability can be achieved.

[0107] With respect to the total weight of the photosensitive resin composition, the content of the thiol compound having an ether bond of the present invention may be 0.5 to 25% by weight, preferably 1 to 9% by weight, and more preferably 1 to 6% by weight. If the content is lower than the above content, problems such as swelling and film shrinkage may occur when exposed to the stripping solution in the subsequent process. If the content is higher than the above content, residues may be generated due to the inability of the unexposed portion to dissolve in the developer, and problems such as reduced resolution may occur.

[0108] (E) Solvent

[0109] In the present invention, as long as the (E) solvent is effective in dissolving other components contained in the photosensitive resin composition of the present invention, solvents used in ordinary photosensitive resin compositions can be used without particular limitation, and ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, etc. are particularly preferred.

[0110] Specific examples of the above solvents include: ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc.

[0111] From the viewpoints of coatability and drying property, the above solvents are preferably organic solvents having a boiling point of 100°C to 200°C, and 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. can be more preferably used.

[0112] The above solvents can be used alone or in combination of two or more.

[0113] The content of the above solvents can be an amount such that the total weight of the photosensitive resin composition becomes 100% by weight. Specifically, the meaning of "balance" in the present invention is the balance such that the total weight of the composition containing the essential components and additional components of the present invention becomes 100% by weight, and the composition of the present invention is not limited by the meaning of the above "balance" not to contain additional components. For example, it can be 10 to 90% by weight, preferably 20 to 75% by weight, based on the total weight of the photosensitive resin composition of the present invention. When the content of the above solvents is within the above range, when coating is carried out using coating devices such as a roll coater, a spin coater, a slot spin coater, a slot coater (sometimes also called a die coater), an inkjet printer, etc., an effect of improved coatability will be provided.

[0114] Other additives

[0115] In addition to the above components, the photosensitive resin composition of the present invention may also contain additives, within the scope that does not impair the object of the present invention, according to the needs of those skilled in the art to improve the coatability, adhesion, etc. of the cured film. For this purpose, components generally used in the art may also be included, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and / or anti-gelling agents, etc. In addition, additives commonly used in the technical field to which the present invention pertains may be further included. They may be used alone or two or more of them may be used in any combination and ratio.

[0116] Specific examples of the above other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

[0117] The above curing agent is used to achieve deep curing and improve mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, etc.

[0118] Specific examples of the epoxy compound among the above 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, novolac 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)acrylic acid glycidyl ester (co)polymers, triglycidyl isocyanurate, etc.

[0119] Specific examples of the oxetane compound among the above curing agents include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexanedicarboxylate dioxetane, etc.

[0120] The above-mentioned curing agent can be used in combination with a co-curing compound, which can cause ring-opening polymerization of the epoxy groups of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the above-mentioned co-curing compound include polycarboxylic acids, polycarboxylic anhydrides, acid generators, etc. The above-mentioned polycarboxylic anhydrides can utilize commercially available epoxy resin curing agents. Specific examples of the above-mentioned epoxy resin curing agents include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Corporation), RIKACID HH (trade name, manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), etc. The above-mentioned exemplified curing agents can be used alone or in combination of two or more.

[0121] The above-mentioned surfactant can be used to further improve the film-forming property of the photosensitive resin composition, and can be added as a silane coupling agent or a leveling agent to improve coatability and adhesion. For example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, etc. can be cited. They can be used alone or in combination of two or more, and it is more preferable to use silicone-based and / or fluorine-based surfactants, but it is not limited thereto.

[0122] Examples of the above-mentioned silicone-based surfactants include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. of GE Toshiba Silicone Co., Ltd. Examples of the above-mentioned fluorine-based surfactants include MEGAFAC F-470, F-471, F-475, F-482, F-489, F-554, etc. of Dainippon Ink and Chemicals, Inc. as commercial products. The above-mentioned exemplified surfactants can be used alone or in combination of two or more.

[0123] Specific examples of the above adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The above-exemplified adhesion promoters can be used alone or in combination of two or more.

[0124] Relative to 100 parts by weight of the total solid content of the photosensitive resin composition, the content of the above adhesion promoter can generally be 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, in terms of weight fraction.

[0125] Specific examples of the above antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, etc.

[0126] Specific examples of the above ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxydibenzophenone, etc.

[0127] Specific examples of the above anticoagulant include sodium polyacrylate, etc.

[0128] Those skilled in the art can appropriately add and use the above additives within the range that does not damage the effects of the present invention. For example, relative to the total weight of the photosensitive resin composition, the above additives can be used in an amount of 0.05 to 10% by weight, preferably 0.1 to 9% by weight, more preferably 0.1 to 8% by weight, but not limited thereto.

[0129] <Pattern>

[0130] The present invention includes a photocured pattern formed on a substrate using the photosensitive resin composition.

[0131] The pattern of the present invention can be manufactured by methods known in the art in addition to being formed from the above photosensitive resin composition. In photo-curing pattern formation, the above photosensitive resin composition can be coated on a substrate and then a pattern can be formed through the steps of exposure and development. At this time, a pre-baking or post-baking process can be carried out between the steps. The heating temperature and heating time of the pre-baking are selected according to the solvent used. For example, it can be carried out at a temperature of 80°C to 100°C for 1 minute to 3 minutes. In the above exposure, an exposure machine is used and exposure is carried out through a photomask, whereby only the part corresponding to the pattern is sensitized. At this time, the light irradiated can be, for example, visible light, ultraviolet light, X-rays, electron rays, etc. At this time, the exposure time is not particularly limited and can be appropriately changed according to the exposure device, the wavelength of the irradiated light, or the exposure amount. However, regarding the preferred exposure time, it can be varied within the range of 5 to 250 seconds.

[0132] Then, as a step of improving the hardness by increasing the adhesion between the patterned film and the substrate, a post-baking can be carried out by performing a heat treatment at the curing temperature for curing, preferably at a temperature of 80 to 100°C for 10 minutes to 120 minutes. The above heat treatment can be carried out using an oven or a hot plate, etc., and is not limited thereto.

[0133] At this time, the thickness of the cured pattern is 3 to 15 μm, and specifically, preferably 5 to 10 μm. If the thickness of the above pattern is below the above range, problems may occur in terms of resolution and patterning. If it is above the above range, problems such as a decrease in transmittance or an impact on optical properties may exist.

[0134] The outgassing generated by the pattern manufactured from the photosensitive resin composition of the present invention is less, the resolution of the mask pattern and / or contact hole pattern is excellent, and the chemical resistance and yellow index (Y.I.) are excellent, thus achieving excellent reliability characteristics. Specifically, in the line / space mask pattern (L / S), the mask width of the minimum dense line pattern is 5 μm or less. In addition, when manufacturing a contact hole from the photosensitive resin composition of the present invention, it is beneficial for manufacturing micro-holes, and micro-holes with a size preferably of 8 μm or less, more preferably 5 μm or less, can be manufactured.

[0135] The clouding and / or haze generation of the pattern made from the photosensitive resin composition of the present invention is suppressed, and physical properties such as flatness, adhesion, and uniformity are improved, thus achieving excellent reliability characteristics. Specifically, the surface roughness of the above-mentioned pattern is 3.0 nm or less, preferably 2.0 nm or less. Even after dry etching, the surface roughness is uniform, and a halftone can be formed. The film thickness of the halftone region (transmission portion with a transmittance of 10%) can be 50% or more, preferably 52% or more, of the film thickness of the full tone region (transmission portion with a transmittance of 100%). Depending on whether a halftone can be formed, it can be used in a curved display. Therefore, there is a continuous need for a halftone function that can generate a height difference according to the mask and / or exposure amount difference, and thus it has the advantages of being able to adjust pattern uniformity and / or surface roughness, etc.

[0136] The above-mentioned pattern can be a photocurable pattern selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern containing a scatterer, and a pattern containing quantum dots.

[0137] The photocurable pattern of the present invention uses a thiol compound having an ether structure to prevent free radicals from being oxygen-blocked during the exposure process, and thus can form a coating film showing excellent development film retention rate, and has the advantages of being able to suppress solvent decomposition to prevent swelling or shrinkage of the coating film and reduction of adhesion when exposed to a stripping solution in a subsequent process.

[0138] <Display device>

[0139] The present invention provides a display device including a pattern made from the above-mentioned photosensitive resin composition.

[0140] Specific examples of the above-mentioned display device include a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device, including OLED and QLED), a flexible display, a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display device for a digital camera, a display device for a navigator, etc., but are not limited thereto.

[0141] The above-mentioned display device may further include components commonly used in the art in addition to the above-mentioned pattern.

[0142] Hereinafter, experimental examples including specific embodiments and comparative examples are provided to help understand the present invention, but it is obvious to those skilled in the art that these are merely illustrative of the present invention and do not limit the scope of the appended claims. Various changes and modifications may be made to the embodiments within the scope of the present invention and the technical concept, and such changes and modifications also fall within the scope of the appended claims. Unless otherwise stated, "%" and "parts" in the examples are "mass %" and "mass parts", respectively.

[0143] <Experimental Example I>

[0144] Synthesis Example 1-1: Production of adhesive resin B1-1

[0145] 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the flask was substituted with nitrogen while stirring, and the temperature was raised to 120°C. Next, a mixture of 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) was added to a monomer mixture consisting of 66.0 g (0.3 mol) of vinyl toluene, 31.2 g (0.3 mol) of styrene and 56.8 g (0.4 mol) of tetrahydrofurfuryl methacrylate was prepared separately. The mixture of the monomer and the polymerization initiator was dripped into the flask from the dropping funnel over 2 hours. After the dripping was completed, the copolymerization reaction was further carried out at 120°C with stirring for 2 hours, thereby generating a resin precursor. Then, the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of butylhydroxytoluene (inhibitor) were added to the above resin precursor solution. After that, the reaction was continued at 110°C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours, thereby obtaining an adhesive resin B1-1 with a double bond equivalent of 450 g / mol. The weight average molecular weight (Mw) of the above adhesive resin B1-1 is 8000, and the solid content acid value is 55 mgKOH / g.

[0146] Synthesis Example 1-2: Production of adhesive resin B1-2

[0147] The same method as in Synthesis Example 1-1 was used to obtain a binder resin B1-2 having a double bond equivalent of 680 g / mol by changing the contents (vinyl toluene 44.0 g (0.2 mole), styrene 20.8 g (0.2 mole) and tetrahydrofurfuryl methacrylate 37.9 g (0.2 mole)). The binder resin B1-2 had a weight average molecular weight (Mw) of 7500 and a solid content acid value of 52 mgKOH / g.

[0148] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120°C. Next, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 44.0 g (0.2 mol) of vinyltoluene, 20.8 g (0.2 mol) of styrene, and 37.9 g (0.2 mol) of tetrahydrofurfuryl methacrylate. The mixture of the monomer and the polymerization initiator was added dropwise to the flask from the dropping funnel over 2 hours. After the dropping was completed, the copolymerization reaction was further carried out by stirring at 120°C for 2 hours to produce a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylhydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. Thereafter, the reaction was continued at 110°C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours.

[0149] Synthesis Example 1-3: Production of adhesive resin B1-3

[0150] The adhesive resin B1-3 at a double bond equivalent level of 900 g / mol was obtained by the same method as in Synthesis Example 1-1 above and by changing the content (66.0 g (0.3 mol) of vinyltoluene, 31.2 g (0.3 mol) of styrene, and 28.4 g (0.2 mol) of tetrahydrofurfuryl methacrylate). The weight average molecular weight (Mw) of the above adhesive resin B1-3 was 8200, and the solid content acid value was 58 mgKOH / g.

[0151] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120°C. Next, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 66.0 g (0.3 mol) of vinyltoluene, 31.2 g (0.3 mol) of styrene, and 28.4 g (0.2 mol) of tetrahydrofurfuryl methacrylate. The mixture of the monomer and the polymerization initiator was added dropwise to the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the copolymerization reaction was further carried out with stirring at 120°C for 2 hours to produce a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylhydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. Thereafter, the reaction was continued at 110°C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours.

[0152] Synthesis Example 1-4: Production of adhesive resin B1-4

[0153] Using the same method as in Synthesis Example 1-1 above and including hexahydrophtalicanhydride in place of tetrahydrophthalic anhydride, an adhesive resin B1-4 with a double bond equivalent of about 420 g / mol was obtained. The weight average molecular weight (Mw) of the above adhesive resin B1-4 was 7900, and the solid content acid value was 55 mgKOH / g.

[0154] Synthesis Example 1-5: Production of adhesive resin B1-5

[0155] Using the same method as in Synthesis Example 1-1 above and including phthalic anhydride in place of tetrahydrophthalic anhydride, an adhesive resin B1-5 with a double bond equivalent of about 560 g / mol was obtained. The weight average molecular weight (Mw) of the above adhesive resin B1-5 was 8100, and the solid content acid value was 56 mgKOH / g.

[0156] Synthesis Example 1-6: Production of adhesive resin B1-6

[0157] Using the same method as in Synthesis Example 1-1 above and including methacrylic anhydride in place of tetrahydrophthalic anhydride, an adhesive resin B1-6 with a double bond equivalent of about 560 g / mol was obtained. The weight average molecular weight (Mw) of the above adhesive resin B1-6 was 8000, and the solid content acid value was 54 mgKOH / g.

[0158] Synthesis Example 1-7: Production of adhesive resin B1-7

[0159] Prepare a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. As the monomer dropping funnel, add 40 parts by weight of a mixture obtained by mixing 3,4-epoxytricyclodec-8-yl (meth)acrylate and 3,4-epoxytricyclodec-9-yl (meth)acrylate at a molar ratio of 50:50, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of tert-butyl peroxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and stir for preparation. As the chain transfer agent dropping tank, add 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA and stir for preparation. Then, add 395 parts by weight of PGMEA to the flask, replace the atmosphere in the flask from air with nitrogen, and while stirring, raise the temperature of the flask to 90 °C. Thereafter, start dropping the monomer and the chain transfer agent from the dropping funnel. During the dropping, while maintaining 90 °C, carry out for 2 hours and 1 hour respectively, then raise the temperature to 110 °C and maintain for 5 hours, thereby obtaining an adhesive resin B1-7 at a double bond equivalent level of 620 g / mol. The weight average molecular weight (Mw) of the above adhesive resin B1-7 is 8200, and the solid component acid value is 100 mgKOH / g.

[0160] Synthesis Example 1-8: Production of thiol compound (pentaerythritol tripropane thiol) T1

[0161] After putting 1.37 mol of pentaerythritol triallyl ether in a round flask, heat it to 40 °C. Drop 4.51 mol of thioacetic acid at a molar ratio of 1:3.3 with pentaerythritol triallyl ether, and then stir the mixed liquid at 40 °C for 4 hours. Add 560 g of 20% aqueous ammonia solution to the reactant, and carry out the reaction at 55 °C for 15 hours. After separating the organic layer, add 490 g of toluene and 350 g of 5% sulfuric acid aqueous solution for washing, then separate and extract the organic layer, and add 350 g of water to the organic layer. Separate, concentrate, and dry the organic layer, thereby synthesizing a colorless transparent oily thiol compound (478 g, yield 98%), and the NMR analysis results are as follows.

[0162] <NMR analysis results of pentaerythritol tripropyl mercaptan>

[0163] 1H-NMR (400 MHz, 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)

[0164] Examples and Comparative Examples: Production of photosensitive resin composition

[0165] The photosensitive resin compositions of the examples and comparative examples were produced according to the composition and weight described in Table 1 below.

[0166] [Table 1]

[0167]

[0168] - B1-1: Adhesive resin produced according to Synthesis Example 1-1

[0169] - B1-2: Adhesive resin produced according to Synthesis Example 1-2

[0170] - B1-3: Adhesive resin produced according to Synthesis Example 1-3

[0171] - B1-4: Adhesive resin produced according to Synthesis Example 1-4

[0172] - B1-5: Adhesive resin produced according to Synthesis Example 1-5

[0173] - B1-6: Adhesive resin produced according to Synthesis Example 1-6

[0174] - B1-7: Adhesive resin produced according to Synthesis Example 1-7

[0175] - M: Dipentaerythritol hexaacrylate (KAYARAD DPHA), manufactured by Nippon Kayaku Co., Ltd.

[0176] - PI: Irgacure OXE-01, manufactured by BASF

[0177] - A: Additive (KBE-9007, Shin-etsu Chemical Co., Ltd.)

[0178] - T1: Ether-based mercaptan compound produced according to Synthesis Example 1-8

[0179] - T2: 1,4-bis(3-mercaptobutylyloxy)butane, manufactured by Showa Denko KK

[0180] - S: Propylene glycol monomethyl ether acetate, manufactured by Sigma-Aldrich

[0181] Experimental Example 1

[0182] Substrate production

[0183] Wash a 5 cm X 5 cm substrate with water and then dry it. The applicable substrates can be glass substrates (Corning Inc.), silicone oxide, or silicone nitride oxide substrates depending on the evaluation method. Spin-coat the photosensitive resin compositions prepared in the above examples and comparative examples on the substrate such that the final film thickness reaches 6.0 μm, and perform pre-baking at 75 - 100 °C for 1 - 3 minutes to remove the solvent by drying. Then, perform exposure at an exposure dose of 40 - 150 mJ / cm 2 to cure it. Subsequently, perform post-baking at 80 - 100 °C for 10 - 120 minutes to fabricate the substrate.

[0184] (1) Outgassing generation

[0185] Cut the fabricated substrate into 1 cm X 1 cm pieces and mount them on an HSS-GC / MS (HT-3, Teledyne Tekmar), and measure the peak area of the generated gas under the conditions of 150 °C for 30 minutes. Set the peak area of Comparative Example 1 as 100% as a reference, and calculate the relative value of the peak area of the gas generated from the cured layer formed using the photosensitive resin compositions of the remaining examples and comparative examples by comparing with it. According to the following evaluation criteria, the results are shown in Table 2 below.

[0186] <Evaluation criteria>

[0187] ◎: 60% or less

[0188] ○: Greater than 60% and 90% or less

[0189] △: Greater than 90% and 120% or less

[0190] Х: Greater than 120%

[0191] (2) Resolution

[0192] During the above substrate fabrication process, use a mask to form a hole pattern during the exposure process, and confirm whether the hole pattern is formed on the finally fabricated substrate through an optical microscope (LV100POL, Nikon). For the size of the hole pattern as the contact hole mask pattern, according to the following evaluation criteria, the results are shown in Table 2 below.

[0193] <Evaluation criteria>

[0194] ◎: 5 μm or less

[0195] ○: Greater than 5 μm and 8 μm or less

[0196] △: Greater than 8 μm and 10 μm or less

[0197] Х: Greater than 10 μm

[0198] (3) Chemical resistance (NMP / Stripper / Etchant)

[0199] The initial film thickness of each substrate was measured (using Dektak6M, manufactured by VEECO) with the substrates fabricated as described above, and the film thickness was measured again after immersion in each solvent. The change in film thickness before and after immersion in the solvent was confirmed, and the chemical resistance was evaluated according to the following evaluation criteria. The results are shown in Table 2 below. The solvents used were N-Methyl-2-pyrolidone (NMP) / Stripper / Etchant. The above-mentioned stripper is of the N-Methyl-2-pyrolidone (NMP) type, and the etchant is an acid type containing nitric acid and sulfuric acid.

[0200] <Evaluation Criteria>

[0201] ◎: The film thickness change rate is less than 0.2 μm

[0202] ○: 0.2 μm or more and less than 0.3 μm

[0203] △: 0.3 μm or more and less than 0.4 μm

[0204] Х: 0.4 μm or more

[0205] (4) Yellow Index (Y.I.)

[0206] The light resistance of the substrates fabricated through the process described above was evaluated. In the light resistance item, an integrating sphere reflectance device (CD-3700D, manufactured by Konica Minolta) was used to measure the Yellow Index (Y.I.). Based on the initial measurement value, the increase or decrease rate was compared by comparing the Y.I. values measured through the additional firing process. The additional firing process was evaluated by performing it 7 times at 230 °C for 30 minutes. According to the following evaluation criteria, the results are shown in Table 2 below.

[0207] <Evaluation Criteria>

[0208] ◎: 2.0 or less

[0209] ○: Greater than 2.0 and 2.5 or less

[0210] △: Greater than 2.5 and 3.0 or less

[0211] Х: Greater than 3.0

[0212] [Table 2]

[0213]

[0214] Based on the experimental data in Table 2 above, in the case of Examples 1-1 to 1-4 of the cured film containing the photosensitive resin composition of the present invention, high-standard results were shown to be satisfied in terms of resolution, suppression of outgassing generation, chemical resistance to NMP, etchant, and stripper, and yellow index evaluation. In addition, in the case of Example 1-5 where the double bond equivalent of the adhesive resin is greater than 700 g / mol, although excellent results were shown in the suppression of outgassing generation and yellow index evaluation, poor results were shown in some evaluations of resolution or chemical resistance compared to other examples.

[0215] On the other hand, in Comparative Examples 1-1, 1-2, and 1-4 where tetrahydrofurfuryl methacrylate and / or a compound having a maleic anhydride structure are not contained during the polymerization of the adhesive resin, and in Comparative Example 1-3 containing an additive of a thiol compound that does not have an ether bond, it was confirmed that most of them could not meet the above evaluation criteria.

[0216] <Experimental Example II>

[0217] Synthesis Example 2-1: Production of adhesive resin B2-1

[0218] 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120°C. Then, a mixture prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 66.0 g (0.3 mol) of vinyltoluene, 31.2 g (0.3 mol) of styrene, and 56.8 g (0.4 mol) of tetrahydrofurfuryl methacrylate was prepared separately. The mixture of the monomer and the polymerization initiator was added dropwise from the dropping funnel to the flask over 2 hours. After the dropping was completed, copolymerization reaction was further carried out by stirring at 120°C for 2 hours to produce a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylhydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. After that, the reaction was continued at 110°C for 10 hours. Then, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask and the reaction was continued at 110°C for 3 hours to obtain Resin B2-1 having a weight average molecular weight (Mw) of 8000 and an acid value of 55 mgKOH / g.

[0219] Synthesis Example 2-2: Production of adhesive resin B2-2

[0220] Using the same method as in Synthesis Example 2-1 above and by changing the amounts (22.0 g (0.1 mol) of vinyltoluene, 10.4 g (0.1 mol) of styrene, and 28.4 g (0.2 mol) of tetrahydrofurfuryl methacrylate)), an adhesive resin B2-2 with a weight-average molecular weight (Mw) of around 4000 was obtained.

[0221] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120 °C. Then, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (a polymerization initiator) to a monomer mixture composed of 22.0 g (0.1 mol) of vinyltoluene, 10.4 g (0.1 mol) of styrene, and 28.4 g (0.2 mol) of tetrahydrofurfuryl methacrylate. This monomer and polymerization initiator mixture was added dropwise from the dropping funnel into the flask over 2 hours. After the addition was complete, the copolymerization reaction was further carried out by stirring at 120 °C for 2 hours to form a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (a catalyst), and 0.6 g of butylhydroxytoluene (a polymerization inhibitor) were added to the above resin precursor solution. After that, the reaction was continued at 110 °C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask and reacted at 110 °C for 3 hours.

[0222] Synthesis Example 2-3: Production of adhesive resin B2-3

[0223] Using the same method as in Synthesis Example 2-1 above and by changing the amounts (110.0 g (0.5 mol) of vinyltoluene, 52.0 g (0.5 mol) of styrene, and 56.8 g (0.4 mol) of tetrahydrofurfuryl methacrylate)), an adhesive resin B2-3 with a weight-average molecular weight (Mw) of around 10000 was obtained.

[0224] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120°C. Next, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 110.0 g (0.5 mol) of vinyltoluene, 52.0 g (0.5 mol) of styrene, and 56.8 g (0.4 mol) of tetrahydrofurfuryl methacrylate. The mixture of the monomer and the polymerization initiator was added dropwise from the dropping funnel into the flask over 2 hours. After the dropping was completed, copolymerization reaction was further carried out with stirring at 120°C for 2 hours to form a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylated hydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. Thereafter, the reaction was continued at 110°C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask and reacted at 110°C for 3 hours.

[0225] Synthesis Example 2-4: Production of adhesive resin B2-4

[0226] Using the same method as in Synthesis Example 2-1 above and by changing the amounts (11.0 g (0.05 mol) of vinyltoluene, 5.2 g (0.05 mol) of styrene, and 7.1 g (0.05 mol) of tetrahydrofurfuryl methacrylate)), an adhesive resin B2-4 with a weight-average molecular weight (Mw) of about 2500 was obtained.

[0227] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120°C. Next, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 11.0 g (0.05 mol) of vinyltoluene, 5.2 g (0.05 mol) of styrene, and 7.1 g (0.05 mol) of tetrahydrofurfuryl methacrylate. The mixture of the monomer and the polymerization initiator was added dropwise from the dropping funnel into the flask over 2 hours. After the dropping was completed, copolymerization reaction was further carried out with stirring at 120°C for 2 hours to form a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylated hydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. Thereafter, the reaction was continued at 110°C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask and reacted at 110°C for 3 hours.

[0228] Synthesis Example 2-5: Production of adhesive resin B2-5

[0229] Using the same method as in Synthesis Example 2-1 and by changing the contents (176.0 g (0.8 mol) of vinyltoluene, 83.2 g (0.8 mol) of styrene, 12.78 g (0.9 mol) of tetrahydrofurfuryl methacrylate, and 114.0 g (0.75 mol) of tetrahydrophthalic anhydride), an adhesive resin B2-5 with a weight-average molecular weight (Mw) of around 19,000 was obtained.

[0230] Specifically, 140 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring, the inside of the flask was purged with nitrogen and heated to 120 °C. Then, a mixture was separately prepared by adding 7.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) to a monomer mixture composed of 176.0 g (0.8 mol) of vinyltoluene, 83.2 g (0.8 mol) of styrene, and 12.78 g (0.9 mol) of tetrahydrofurfuryl methacrylate. The mixture of the monomer and the polymerization initiator was added dropwise from the dropping funnel to the flask over 2 hours. After the dropping was completed, copolymerization was carried out by further stirring at 120 °C for 2 hours to form a resin precursor. Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylhydroxytoluene (polymerization inhibitor) were added to the above resin precursor solution. Thereafter, the reaction was continued at 110 °C for 10 hours. Next, 114.0 g (0.75 mol) of tetrahydrophthalic anhydride was added to the flask and reacted at 110 °C for 3 hours.

[0231] Examples and Comparative Examples: Production of photosensitive resin composition

[0232] The photosensitive resin compositions of the examples and comparative examples were manufactured according to the compositions and weights described in Table 3 below.

[0233] [Table 3]

[0234]

[0235] - B2-1: Adhesive resin manufactured according to Synthesis Example 2-1

[0236] - B2-2: Adhesive resin manufactured according to Synthesis Example 2-2

[0237] - B2-3: Adhesive resin manufactured according to Synthesis Example 2-3

[0238] - B2-4: Adhesive resin manufactured according to Synthesis Example 2-4

[0239] - B2-5: Adhesive resin produced according to Synthesis Example 2-5

[0240] - M: Dipentaerythritol hexaacrylate (KAYARAD DPHA), manufactured by Nippon Kayaku Co., Ltd.

[0241] - PI: Irgacure OXE-01, manufactured by BASF

[0242] - A: KBE-9007 (Shin-Etsu Chemical Co., Ltd.)

[0243] - T1: Ether-based mercaptan compound produced according to Synthesis Example 1-8

[0244] - T3: KarenzMT™ PE1 (Karenz)

[0245] - S: Propylene glycol monomethyl ether acetate, manufactured by Sigma-Aldrich

[0246] Experimental Example 2

[0247] Substrate production

[0248] A 5 cm x 5 cm substrate was washed with water and then dried. Applicable substrates can be glass substrates (Corning Inc.) or silicon oxide or silicon oxynitride substrates depending on the evaluation method. The photosensitive resin compositions manufactured in the above Examples and Comparative Examples were spin-coated onto the substrates such that the final film thickness reached 5.0 μm, and pre-fired at 50 to 100 °C for 1 to 3 minutes to remove the solvent. Then, exposure was carried out at an exposure dose of 40 to 150 mJ / cm 2 to cure. Subsequently, firing was carried out at 80 to 100 °C for 10 to 120 minutes to fabricate the substrate.

[0249] (1) Surface roughness

[0250] For the substrates fabricated above, the surface roughness (Ra) was measured using an AFM device (NX10, Park Systems XE-100). Specifically, the measurement was carried out in the contact mode with a measurement range of 10 x 10 μm. According to the following evaluation criteria, the results are shown in Table 4 below.

[0251] <Evaluation criteria>

[0252] ◎: 3.0 nm or less

[0253] ○: Greater than 3.0 nm and 5.0 nm or less

[0254] △: Greater than 5.0 nm and 7.0 nm or less

[0255] X: Greater than 7.0 nm

[0256] (2) Cloudiness

[0257] Using the substrate fabricated above, metal (Metal, type: ITO) evaporation was carried out using an ITO evaporation apparatus (SMD650C (Ulvac)). The condition was to carry out evaporation at a thickness of 5000 Å under normal temperature conditions. After evaporation, visually confirm whether there is cloudiness using light reflection. According to the following evaluation criteria, the results are shown in Table 4 below.

[0258] <Evaluation Criteria>

[0259] ◎: No cloudiness

[0260] X: Cloudiness occurs

[0261] (3) Haze

[0262] For the substrate fabricated above, measurement was carried out using a haze meter (Haze Meter, HM - 150, Murakami). Taking the blank value before measurement as 100 as a reference, the degree of haze generation of the coating film was evaluated according to the following evaluation criteria. The results are shown in Table 4 below.

[0263] <Evaluation Criteria>

[0264] ◎: 0.5 or less

[0265] ○: Greater than 0.5 and 1.0 or less

[0266] △: Greater than 1.0 and 1.2 or less

[0267] X: Greater than 1.2

[0268] (4) Planarity evaluation (DOP, Degree of Planarization)

[0269] This is an evaluation method using a substrate having a certain lower pattern on a substrate. A substrate having a certain pattern on a substrate was fabricated, and the composition described in the present invention was coated on this substrate via the above substrate fabrication process. DOP evaluation was carried out using the height of a certain lower pattern and the overall height after coating the composition described in the present invention. The relevant formula is the same as Formula 1 below. In height measurement, SNU (SUN, SIS - 2000) was used for measurement. According to the evaluation criteria, the values are shown in Table 4 below.

[0270] <Formula 1>

[0271] DOP(%) = [{Lower pattern height - (Overall height - Height of the composition of the present invention from the substrate)} / Lower pattern height] x 100

[0272] <Evaluation criteria>

[0273] ◎: 40% or less

[0274] ○: Greater than 40% and 50% or less

[0275] △: Greater than 50% and 70% or less

[0276] Х: Greater than 70%

[0277] (5) Adhesion evaluation (Cross Cut)

[0278] Use a cutter to score the substrate made above to form a 10x10 grid on the coating. Then, cover the coating with tape and immediately peel it off, and then confirm the number of remaining grids and the peeling level of the coating. The above evaluation is based on the ASTM D3359 evaluation method, as shown in Table 4 below.

[0279] <Evaluation criteria>

[0280] ◎: 5B or less

[0281] ○: 4B or more

[0282] △: 3B or more

[0283] Х: Less than 3B

[0284] (6) H / T (half-tone)

[0285] In the process of manufacturing the above substrate, a negative mask capable of achieving 100% transmission part and 10% transmission part is intervened. Specifically, after coating a photosensitive resin composition on a 5 Х 5 cm glass substrate and drying it, bar coating is carried out to a thickness of 2.5 μm. Then, after drying in an oven at 100 °C for 3 minutes to remove the solvent, the distance from it to the photomask is set to 300 μm, and after exposure with a cumulative light amount of 40 mJ at a wavelength of 313 nm of a FUSION lamp, it is immersed in a KOH aqueous solution with pH 14 for 3 minutes respectively and then taken out, immersed in distilled water again for 1 minute and then taken out, and then cured in an oven at 230 °C for 20 minutes to manufacture a substrate formed with a halftone pattern. For the manufactured pattern, the heights of the 100% transmission part (100T%) and the 10% transmission part (10T%) are measured using an SEM device (JSM-7900F, JEOL), and the height ratio of the 10% transmission part (10T%) based on the height of the 100% transmission part (100T%) is as shown in Table 4 below. At this time, only when the height difference is small can the pattern uniformity and thickness be adjusted, so the pattern that meets this point is judged to be excellent.

[0286] [Table 4]

[0287]

[0288] According to the experimental data in Table 4 above, in the case of Examples 2-1 to 2-5 of the cured film containing the photosensitive resin composition of the present invention, in the evaluations of surface roughness, white turbidity, haze, flatness (DOP), adhesion (cross-cut), and halftone height, all showed results that met high standards. In particular, since it was confirmed that the halftone height ratio of the 10% transmission part (10T%) based on the height of the 100% transmission part (100T%) was as high as 52% or more, the pattern uniformity was shown to be excellent. In addition, in the case of Examples 2-6 and 2-7 where the weight ratio of the binder resin to the photocurable compound deviated from 4:6 to 6:4, although the surface roughness and white turbidity characteristics were excellent, in some evaluations of haze, flatness (DOP), adhesion (cross-cut), and halftone height, the results were shown to be worse than those of other examples.

[0289] On the other hand, in the case of Comparative Example 2-1 where the weight average molecular weight of the binder resin was less than 4000, Comparative Example 2-2 where the weight average molecular weight of the binder resin was greater than 15000, and Comparative Example 2-3 containing an additive of a thiol compound not having an ether bond, it was confirmed that most of them could not meet the above evaluation criteria or the halftone height ratio was as low as 38% or less.

Claims

1. A photosensitive resin composition, characterized in that, comprising (A) an adhesive resin, (B) a photocurable compound, (C) an initiator, (D) an additive, and (E) a solvent, the (A) adhesive resin is obtained by polymerizing a compound comprising tetrahydrofurfuryl methacrylate and a compound having a maleic anhydride structure, the weight average molecular weight Mw of the (A) adhesive resin is 4,000 to 15,000, the (D) additive comprises a thiol compound having an ether bond.

2. The photosensitive resin composition according to claim 1, wherein the compound having a maleic anhydride structure further has a hydrocarbon ring structure having 3 to 20 carbon atoms.

3. The photosensitive resin composition according to claim 2, wherein the compound having a maleic anhydride structure has a condensed bicyclic hydrocarbon ring structure having 6 to 16 carbon atoms.

4. The photosensitive resin composition according to claim 3, wherein the compound having a maleic anhydride structure is one or more selected from methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and phthalic anhydride.

5. The photosensitive resin composition according to claim 1, wherein the double bond equivalent of the (A) adhesive resin is 700 g / mol or less.

6. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight Mw of the (A) adhesive resin is 4,000 to 10,000.

7. The photosensitive resin composition according to claim 1, wherein The acid value of the (A) adhesive resin is 20 mgKOH / g to 100 mgKOH / g.

8. The photosensitive resin composition according to claim 1, wherein in the total weight of the composition, the weight ratio of the (A) adhesive resin:(B) photocurable compound is 4:6 to 6:

4.

9. The photosensitive resin composition according to claim 1, wherein The thiol compound having an ether bond is represented by the following Chemical Formula 1 or Chemical Formula 2: Chemical Formula 1 Chemical Formula 2 In the Chemical Formulas 1 to 2, R1 is a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups -SH, R2 to R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more thiol groups -SH.

10. The photosensitive resin composition according to claim 1, wherein The thiol compound having an ether bond is represented by the following Chemical Formula 3 or Chemical Formula 4: Chemical Formula 3 In the Chemical Formula 3, R5 is an alkylene group having 1 to 10 carbon atoms, m1 and n1 are each independently an integer of 1 to 3, and m1 + n1 = 4, Chemical Formula 4 In the Chemical Formula 4, R6 are each independently an alkylene group having 1 to 10 carbon atoms, m2, m3, n2, and n3 are each independently an integer of 1 to 3, and m2 + n2 = 3, m3 + n3 = 3.

11. The photosensitive resin composition according to claim 1, which cures at 100°C or lower.

12. A pattern comprising a cured product of the photosensitive resin composition according to claim 1.

13. The pattern according to claim 12, wherein the thickness of the pattern after curing is 5 to 10 μm, and exhibits pore characteristics of 5 μm or less.

14. The pattern according to claim 12, wherein, The film thickness of the halftone region of the pattern is 50% or more of the film thickness of the full tone region.

15. The pattern according to claim 12, wherein the pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, a black column spacer, a color resist pattern, a pattern containing a scatterer, and a pattern containing quantum dots.

16. A display device comprising the pattern according to claim 12.

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