Photosensitive resin composition, photosensitive resin film using the same, display device, and method for producing photosensitive resin film

Abstract

To provide a photosensitive resin composition which is sufficiently cured even at low temperature, is transparent, is excellent in adhesive force to a color filter, and is excellent in developability and fine patterning property.SOLUTION: A photosensitive resin film contains (A) a polymer resin having a refractive index of 1.66 or more, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a solvent, wherein the polymer resin has a repeating structural unit, and the structural unit includes a residue derived from an acid dianhydride. The structural unit may further contain a residue containing one or more sulfur atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film using the same, a display device, and a method for producing the photosensitive resin film. [Background technology]

[0002] Recently, there has been growing interest in self-luminous micro OLED display panels, which emit light themselves, as display panels applied to VR (Virtual Reality), AR (Augmented Reality), and MR (Mixed Reality) devices.

[0003] In the case of micro OLED display panels, which have pixel size about 10 times smaller than that of general OLED display panels, it is difficult to precisely form red (R), green (G), and blue (B) light-emitting layers using existing FMM (Fine Metal Mask) technology. In other words, when applying existing LCD displays to devices such as VR and AR, the color filter pattern size is too large, making it difficult to increase resolution.

[0004] Recently, OLEDos (OLED on Silicon) technology has been introduced to achieve high resolutions of over 4000 ppi. This technology uses an OLED deposited on a silicon wafer as a backlight, on which a color filter is patterned. Conventional color filters used in LCDs have a pattern of approximately 100 μm placed on glass, which is then exposed to light and hardened through a post-bake process at a high temperature of over 230°C. However, the color filters placed on OLEDos cannot undergo high-temperature processes due to the nature of OLEDs, so they must be hardened at low temperatures. Furthermore, fine patterning is also essential to achieve the desired resolution. Due to the small size of VR, AR, and MR devices, fine patterning is essential to achieve the desired resolution within these devices.

[0005] However, since they can only be cured at low temperatures (below 100°C), color filters made from existing materials have problems with poor developability and patterning. Therefore, research is being conducted on transparent materials that can be cured at low temperatures and have excellent color filter adhesive strength, developability, and fine patterning properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Korean Patent Publication No. 2016-0000102 Summary of the Invention [Problem to be solved by the invention]

[0007] One embodiment of the present invention provides a photosensitive resin composition that cures sufficiently even at low temperatures, is transparent, has excellent adhesion to color filters, and is excellent in developability and fine patternability.

[0008] Another embodiment of the present invention provides a photosensitive resin film prepared using the photosensitive resin composition.

[0009] Yet another embodiment of the present invention provides a display device including the photosensitive resin film.

[0010] Yet another embodiment of the present invention provides a method for producing the photosensitive resin film. [Means for solving the problem]

[0011] One embodiment of the present invention provides a photosensitive resin composition comprising: (A) a polymer resin having a refractive index of 1.66 or greater; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a solvent, wherein the polymer resin has a repeating structural unit, and the structural unit includes a residue derived from an acid dianhydride.

[0012] The structural unit may further include a residue containing one or more sulfur atoms.

[0013] The residue containing one or more sulfur atoms can include structures represented by the following Chemical Formulas 1 to 3.

[0014] [ka] chemical formula 1

[0015] [ka] chemical formula 2

[0016] [ka] chemical formula 3

[0017] In the above Chemical Formulas 1 to 3, X is * -S- * or * -S(=O)2- * and R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L 1 ~L 6 are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

[0018] The residue containing one or more sulfur atoms may include at least one structure selected from the group consisting of Chemical Formula 1-1, Chemical Formula 1-2, Chemical Formula 2-1, and Chemical Formula 3-1 below.

[0019] [ka] Chemical formula 1-1

[0020] [ka] Chemical formula 1-2

[0021] [ka] Chemical formula 2-1

[0022] [ka] Chemical formula 3-1

[0023] The residue derived from the acid dianhydride may include a structure represented by the following formula 4-1 or 4-2.

[0024] [ka] Chemical formula 4-1

[0025] [ka] Chemical formula 4-2

[0026] In the above Chemical Formula 4-1 and Chemical Formula 4-2, Y is a single bond or * -C(=O)- * is.

[0027] The repeating structural unit in the polymer resin is represented by any one of the following formulas 5 to 8.

[0028] [ka] chemical formula 5

[0029] [ka] chemical formula 6

[0030] [ka] chemical formula 7

[0031] [ka] chemical formula 8

[0032] The polymer resin may be included in an amount of 10% by weight to 30% by weight based on the total amount of the photosensitive resin composition.

[0033] The polymer resin may have a weight average molecular weight of 2,000 g / mol to 20,000 g / mol.

[0034] The photosensitive resin composition can contain, relative to the total amount of the photosensitive resin composition, 10% by weight to 30% by weight of the (A) polymer resin, 3% by weight to 15% by weight of the (B) photopolymerizable monomer, 0.1% by weight to 5% by weight of the (C) photopolymerization initiator, and a remaining amount of the (D) solvent.

[0035] The photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a polymerization inhibitor, or a combination thereof.

[0036] The photosensitive resin composition may have a refractive index of 1.62 or greater.

[0037] Another embodiment of the present invention provides a photosensitive resin film prepared using the photosensitive resin composition.

[0038] The photosensitive resin film may be transparent.

[0039] Yet another embodiment of the present invention provides a display device including the photosensitive resin film.

[0040] The display device may be a micro OLED display device including an OLED substrate deposited on a silicon wafer and a color filter layer located on the OLED substrate and converting white light generated from the OLED substrate into a plurality of color lights, wherein the photosensitive resin film is located on the OLED substrate and the color filter layer, and the color filter layer includes a red color filter, a green color filter, and a blue color filter.

[0041] Yet another embodiment of the present invention provides a method for manufacturing a photosensitive resin film, including: applying the photosensitive resin composition; pre-baking the applied photosensitive resin composition at a temperature of 100°C or less; exposing the pre-baked photosensitive resin composition to an i-line; and developing the photosensitive resin film.

[0042] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0043] The photosensitive resin composition according to one embodiment of the present invention is a transparent photosensitive resin composition that can be cured at a low temperature of 100°C or less, has excellent adhesion to a color filter, and is excellent in developability and fine patterning. The above-mentioned effects can be achieved only by pre-baking at a temperature of 100°C or less and photo-curing (i-line exposure), and can be suitably used as a micro lens array in a micro OLED display device that can realize fine patterns. [Brief explanation of the drawings]

[0044] [Figure 1] 1 is a schematic diagram illustrating the structure of a micro OLED display device according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0045] DETAILED DESCRIPTION OF THE INVENTION The following detailed description of the preferred embodiments of the present invention is provided by way of example only and is not intended to limit the scope of the present invention, which is defined solely by the scope of the claims that follow.

[0046] Unless otherwise specified, in this specification, an "alkyl group" means an alkyl group having 1 to 20 carbon atoms, an "alkenyl group" means an alkenyl group having 2 to 20 carbon atoms, a "cycloalkenyl group" means a cycloalkenyl group having 3 to 20 carbon atoms, a "heterocycloalkenyl group" means a heterocycloalkenyl group having 3 to 20 carbon atoms, an "aryl group" means an aryl group having 6 to 20 carbon atoms, an "arylalkyl group" means an arylalkyl group having 6 to 20 carbon atoms, an "alkylene group" means an alkylene group having 1 to 20 carbon atoms, an "arylene group" means an arylene group having 6 to 20 carbon atoms, an "alkylarylene group" means an alkylarylene group having 6 to 20 carbon atoms, a "heteroarylene group" means a heteroarylene group having 3 to 20 carbon atoms, and an "alkoxysilane group" means an alkoxysilane group having 1 to 20 carbon atoms.

[0047] Unless otherwise specified in this specification, "substituted" means that at least one hydrogen atom has been replaced with a halogen atom (F, Cl, Br, I), a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amino group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, an alkyl group having 1 to 20 carbon atoms, a carbon atom, a It means being substituted with an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, a heterocycloalkenyl group having 2 to 20 carbon atoms, a heterocycloalkynyl group having 2 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a combination thereof.

[0048] In addition, unless otherwise specified in this specification, "hetero" means that at least one heteroatom selected from N, O, S, and P is contained in the chemical formula.

[0049] Furthermore, unless otherwise specified in this specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means that both "acrylic acid" and "methacrylic acid" are possible.

[0050] Unless otherwise defined herein, "combination" means a mixture or copolymerization, and "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

[0051] In the chemical formulas herein, unless otherwise defined, if no chemical bond is drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bound to that position.

[0052] Unless otherwise defined herein, "*" means a moiety connected to the same or different atom or chemical formula.

[0053] A photosensitive resin composition according to one embodiment includes: (A) a polymer resin having a refractive index of 1.66 or greater; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a solvent, wherein the polymer resin has a repeating structural unit, and the structural unit includes a residue derived from an acid dianhydride.

[0054] Conventional color photoresists are negative-type photosensitive liquid materials that realize red, green, and blue color patterns, and technological developments have been directed toward gradually changing the composition of the liquid materials. For example, efforts have been made to improve color purity by changing the type and content of the pigment dispersion liquid, which is the coloring material that realizes the color patterns, to improve patterning by changing the composition of the binder resin or photopolymerization initiator, or to improve coating properties and color uniformity by using other additives such as leveling agents.

[0055] The present invention is not directed to a color photoresist used in manufacturing conventional color filters, but to a microlens applied to a Micro OLED display device. The microlens has excellent adhesion to low-temperature curing color filters and can be applied to display devices including the low-temperature curing color filters.

[0056] A micro display is a technology that transmits image information using an optical system to a display with a screen size of 1 inch or less. Since high resolution must be achieved in an extremely small area, a CMOS backplane on a Si wafer substrate is used. Among them, a micro OLED display uses OLED as the backlight for light emission, so a low-temperature curing color filter is required. Meanwhile, as pixel size becomes smaller, highly sensitive materials are required for accurate color reproduction.

[0057] In the existing semiconductor CMOS process, HDMS deposition is used to bond color filters, but this does not allow for low-temperature curing. To solve this problem, much research has been conducted into alternative materials. After extensive research, the inventors have developed a photosensitive resin composition for microlenses that can be cured at low temperatures and has excellent developability and fine patterning properties, leading to the completion of the present invention.

[0058] Specifically, the photosensitive resin composition according to one embodiment is a low-temperature curable, transparent material that exhibits high adhesion to color filters, minimal residue (excellent developability), and excellent pattern linearity (excellent fine patterning). In particular, the transparent material makes it suitable for use in next-generation display devices such as VR (Virtual Reality), AR (Augmented Reality), and MR (Mixed Reality), which require transparency (crack prevention) and precise patterning to fit desired areas, such as micro OLED display devices. That is, the photosensitive resin composition according to one embodiment may be a colorant-free composition, e.g., a transparent photosensitive resin composition, and therefore exhibits excellent transmittance.

[0059] More specifically, in the photosensitive resin composition according to one embodiment, the refractive index of the polymer resin, specifically, the refractive index of the polymer resin at 550 nm, can be controlled to 1.66 or more, thereby improving residue characteristics (developability) and pattern linearity (fine patterning).

[0060] Each component will be specifically described below.

[0061] (A) Polymer resin As described above, the photosensitive resin composition according to one embodiment includes a polymer resin, and the residual characteristics, pattern linearity, and adhesion strength to a color filter can be significantly improved by controlling the refractive index of the polymer resin at 550 nm. Specifically, the refractive index of the polymer resin at 550 nm can be controlled to 1.66 to 1.8, for example, 1.66 to 1.75, for example, 1.66 to 1.7, for example, 1.67 to 1.8, for example, 1.68 to 1.8.

[0062] In order to control the refractive index at 550 nm as described above, the polymer resin in the photosensitive resin composition according to one embodiment includes a repeating structural unit, and the structural unit may include two residues, for example, a "residue derived from an acid dianhydride" and a "residue containing one or more sulfur atoms." For example, the residue containing one or more sulfur atoms may include two or more sulfur atoms, for example, three or more sulfur atoms, for example, four or more sulfur atoms. The greater the number of sulfur atoms, the higher the refractive index of the polymer resin at 550 nm, thereby maximizing the aforementioned improvements in developability and pattern linearity.

[0063] On the other hand, the polymer resin necessarily contains the "residue derived from an acid dianhydride." If the polymer resin contains only the "residue containing one or more sulfur atoms," it becomes difficult to control the refractive index at 550 nm to 1.66 or more, which may result in significantly poor developability and pattern linearity. Furthermore, the resin must be a polymer resin. When a monomolecular resin is used, even if the refractive index at 550 nm is controlled within the above range, it is a monomolecular resin, and therefore may have poor compatibility with other components, such as photopolymerizable monomers and photopolymerization initiators, resulting in significantly poor developability and pattern linearity.

[0064] For example, the residue containing one or more sulfur atoms may include structures represented by the following Chemical Formulas 1 to 3, but is not necessarily limited thereto.

[0065] [ka] chemical formula 1

[0066] [ka] chemical formula 2

[0067] [ka] chemical formula 3

[0068] In the above Chemical Formulas 1 to 3, X is * -S- * or * -S(=O)2- * and R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L 1 ~L 6 are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

[0069] For example, the residue containing one or more sulfur atoms may include at least one structure selected from the group consisting of Chemical Formula 1-1, Chemical Formula 1-2, Chemical Formula 2-1, and Chemical Formula 3-1 below, but is not necessarily limited thereto.

[0070] [ka] Chemical formula 1-1

[0071] [ka] Chemical formula 1-2

[0072] [ka] Chemical formula 2-1

[0073] [ka] Chemical formula 3-1

[0074] For example, the residue derived from the acid dianhydride may include a structure represented by the following Chemical Formula 4-1 or 4-2.

[0075] [ka] Chemical formula 4-1

[0076] [ka] Chemical formula 4-2

[0077] In the above Chemical Formula 4-1 and Chemical Formula 4-2, Y is a single bond or * -C(=O)- * is.

[0078] For example, the repeating structural unit in the polymer resin may be represented by any one of the following formulas 5 to 8, but is not limited thereto.

[0079] [ka] chemical formula 5

[0080] [ka] chemical formula 6

[0081] [ka] chemical formula 7

[0082] [ka] chemical formula 8

[0083] For example, the polymer resin may be included in an amount of 10 wt % to 30 wt %, for example, 15 wt % to 25 wt %, based on the total amount of the photosensitive resin composition. For example, the polymer resin may be included in an amount of 40 wt % to 80 wt %, for example, 50 wt % to 70 wt %, based on the total amount of solids comprising the photosensitive resin composition. When the weight of the polymer resin is controlled within the above range, the difference between the refractive index at 550 nm of the photosensitive resin composition according to one embodiment and the refractive index of the polymer resin at 550 nm can be minimized, ultimately maximizing improvements in the developability and pattern linearity of the photosensitive resin composition.

[0084] For example, the polymer resin may have a weight-average molecular weight of 20,000 g / mol to 80,000 g / mol. By controlling the weight-average molecular weight of the polymer resin within the above range, the polymer resin has excellent compatibility with the photopolymerizable monomer and photopolymerization initiator, which are other components described below.

[0085] Meanwhile, the photosensitive resin composition according to an embodiment may further include, in addition to the polymer resin, a binder resin that has been conventionally used, such as an acrylic binder resin, an epoxy binder resin, or a combination thereof.

[0086] The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

[0087] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0088] The first ethylenically unsaturated monomer may be contained in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight, based on the total amount of the acrylic binder resin.

[0089] Examples of the second ethylenically unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These may be used alone or in combination.

[0090] Specific examples of the acrylic binder resin include, but are not limited to, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like. These may be used alone or in combination of two or more.

[0091] The acrylic binder resin may have an acid value of 30 KOHmg / g to 180 KOHmg / g and a weight average molecular weight of 3,000 g / mol to 20,000 g / mol. When the acid value and weight average molecular weight of the acrylic binder resin are within the above ranges, the resulting thin film may have excellent pattern formability and excellent mechanical and thermal properties.

[0092] When the epoxy-based binder resin is further included in the photosensitive resin composition according to an embodiment, heat resistance can be improved. Examples of the epoxy-based binder resin include, but are not limited to, phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, and combinations thereof.

[0093] (B) Photopolymerizable monomer The photopolymerizable monomer in the photosensitive resin composition according to one embodiment may be a single compound or a mixture of two different compounds.

[0094] For example, the photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0095] The photopolymerizable monomer has the ethylenically unsaturated double bond, and thus undergoes sufficient polymerization upon exposure in the pattern formation process, thereby forming a pattern with excellent heat resistance, light resistance, and chemical resistance.

[0096] Specific examples of the photopolymerizable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, Examples of the epoxy (meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, ethoxylated bisphenylfluorene diacrylate, ethoxylated naphthalene type diacrylate, and ethoxylated sulfur type diacrylate.

[0097] Examples of commercially available products of the photopolymerizable monomer are as follows: Examples of the monofunctional ester of (meth)acrylic acid include Aronix M-101 (registered trademark), M-111 (registered trademark), M-114 (registered trademark), etc., manufactured by Toagosei Chemical Industry Co., Ltd., KAYARAD TC-110S (registered trademark), TC-120S (registered trademark), etc., manufactured by Nippon Kayaku Co., Ltd., and V-158 (registered trademark), V-2311 (registered trademark), etc., manufactured by Osaka Organic Chemical Industry Ltd. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M-210 (registered trademark), M-240 (registered trademark), and M-6200 (registered trademark), manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA (registered trademark), HX-220 (registered trademark), and R-604 (registered trademark), manufactured by Nippon Kayaku Co., Ltd.; V-260 (registered trademark), V-312 (registered trademark), and V-335 HP (registered trademark), manufactured by Osaka Organic Chemical Industry Co., Ltd.; and BPF-022, BPF-022B, BPF-022L, BPF-022G, BPF-102, BPF-152, BPF-202, BPF-302, BN-042, BN-102, TBP-042, and TBP-102, manufactured by Hannong Chemical Co., Ltd. Examples of the trifunctional esters of (meth)acrylic acid include Aronix M-309 (registered trademark), M-400 (registered trademark), M-405 (registered trademark), M-450 (registered trademark), M-710 (registered trademark), M-8030 (registered trademark), and M-8060 (registered trademark), manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD TMPTA (registered trademark), DPCA-20 (registered trademark), DPCA-30 (registered trademark), DPCA-60 (registered trademark), and DPCA-120 (registered trademark), manufactured by Nippon Kayaku Co., Ltd.; and V-295 (registered trademark), V-300 (registered trademark), V-360 (registered trademark), V-GPT (registered trademark), V-3PA (registered trademark), and V-400 (registered trademark), manufactured by Osaka Organic Chemical Industry Co., Ltd. These products can be used alone or in combination of two or more.

[0098] The photopolymerizable monomer may be treated with an acid anhydride to provide better developability.

[0099] For example, the photopolymerizable monomer may be contained in an amount of 3 wt% to 15 wt%, e.g., 5 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. For example, the photopolymerizable monomer may be contained in an amount of 20 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, sufficient curing occurs upon exposure in the pattern formation step, resulting in excellent reliability and excellent developability in an alkaline developer.

[0100] (C) Photopolymerization initiator According to an embodiment, the photosensitive resin composition includes a photopolymerization initiator, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

[0101] Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0102] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0103] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0104] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0105] Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

[0106] Examples of the oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0107] In addition to the above compounds, the photopolymerization initiator may also include carbazole-based compounds, diketone compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, non-imidazole-based compounds, and fluorene-based compounds.

[0108] For example, the photopolymerization initiator may be contained in an amount of 0.1 wt % to 5 wt %, e.g., 0.5 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. For example, the photopolymerization initiator may be contained in an amount of 1 wt % to 5 wt %, e.g., 1.5 wt % to 3 wt %, based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, sufficient photopolymerization occurs upon exposure in the pattern formation step for manufacturing microlenses, resulting in excellent sensitivity and improved transmittance.

[0109] (D) Solvent The solvent may be a substance that is compatible with but does not react with the polymer resin, the photopolymerizable monomer, and the photopolymerization initiator.

[0110] Examples of the solvent include alcohols such as methanol and ethanol, ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate, carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl ketones such as methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters such as methyl lactate, ethyl lactate, etc.; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-hydroxypropionic acid methyl ester alkyl 3-oxypropionates such as ethyl 3-oxypropionate, alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate, alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate, alkyl 2-oxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and ethyl 2-ethoxypropionate,2-alkoxypropionic acid alkyl esters such as methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate; Examples of suitable solvents include ketone acid esters such as ethyl pyruvate, and high-boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0111] Of these, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, esters such as ethyl 2-hydroxypropionate, carbitols such as diethylene glycol monomethyl ether, and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be preferably used.

[0112] For example, the solvent may be contained in an amount of, for example, 50% by weight to 90% by weight, for example, 60% by weight to 80% by weight, or for example, 70% by weight to 80% by weight relative to the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, thereby providing excellent processability during the production of a photosensitive resin film, specifically, a microlens.

[0113] (E) Other additives Meanwhile, the photosensitive resin composition may further include an additive such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a polymerization inhibitor, or a combination thereof.

[0114] The silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to a substrate, etc. However, even if a silane coupling agent is used, since the photosensitive resin composition according to one embodiment is a colorant-free composition, i.e., a transparent photosensitive resin composition, if the refractive index at 550 nm of the polymer resin is not controlled as described above, the effect of improving adhesion to a color filter may not be obtained.

[0115] Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, which can be used alone or in combination of two or more.

[0116] The silane coupling agent may be contained in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the composition has excellent adhesion, storage stability, and the like.

[0117] In addition, the photosensitive resin composition may further contain a surfactant, for example, a fluorine-based surfactant and / or a silicone-based surfactant, to improve coating properties and prevent defects, if necessary.

[0118] Examples of the fluorine-based surfactant include BM-1000 (registered trademark) and BM-1100 (registered trademark) manufactured by BM Chemie, and Megafac F 142D (registered trademark), F 172 (registered trademark), F 173 (registered trademark), F 183 (registered trademark), F 554 (registered trademark), and F 555 (registered trademark) manufactured by Dainippon Ink and Chemicals, Inc. 556 (registered trademark), etc.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark), etc. manufactured by Sumitomo 3M Limited; Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark), etc. manufactured by Asahi Glass Co., Ltd.; SH-28PA (registered trademark), S-190 (registered trademark), S-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc. manufactured by Toray Silicon Co., Ltd. can be used.

[0119] As the silicone surfactant, commercially available products manufactured by BYK Chem under the names BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, etc. can be used.

[0120] The surfactant can be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is used in an amount within the above range, coating uniformity is ensured, no unevenness occurs, and excellent wetting is achieved on IZO substrates or glass substrates.

[0121] The polymerization inhibitor may include, but is not limited to, a catechol-based compound. When the photosensitive resin composition according to an embodiment further includes the catechol-based compound, room temperature crosslinking can be prevented during exposure after coating the photosensitive resin composition.

[0122] For example, the catechol-based compound may include, but is not limited to, catechol, t-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol, and tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum.

[0123] The catechol-based compound can be used in the form of a dispersion, and the polymerization inhibitor in the dispersion form can be contained in an amount of 0.001 to 3% by weight, for example, 0.01 to 1% by weight, based on the total amount of the photosensitive resin composition. When the polymerization inhibitor is contained within the above range, it can solve the problem of aging at room temperature and prevent sensitivity reduction and surface peeling.

[0124] The photosensitive resin composition may contain a certain amount of other additives such as stabilizers within the range that does not impair the physical properties.

[0125] The photosensitive resin composition according to an embodiment may be a positive type or a negative type, but is preferably a negative type in order to more completely remove residues in areas where a pattern is exposed after exposure and development of a composition having light-blocking properties.

[0126] Meanwhile, the photosensitive resin composition according to one embodiment may have a refractive index (at 550 nm) of 1.62 or more, for example, a refractive index (at 550 nm) of 1.62 or more but less than 1.66. When the refractive index at 550 nm of the photosensitive resin composition containing the polymer resin is controlled as described above, it is advantageous for improving developability and fine patterning.

[0127] Another embodiment provides a photosensitive resin film manufactured by low-temperature curing, exposing, and developing the above-described photosensitive resin composition. This method is different from conventional LCD and semiconductor processes in that it does not require a post-curing (post-baking) process.

[0128] The photosensitive resin film is produced as follows.

[0129] (1) Coating and film formation stage (low-temperature curing) The photosensitive resin composition is applied to a substrate such as a silicon wafer that has been pretreated to a desired thickness using methods such as spin or slit coating, roll coating, screen printing, or applicator, and then heated at 100°C for 1 to 10 minutes to remove the solvent, forming a photosensitive resin film. This step can improve image quality unevenness.

[0130] (2) Exposure stage To form the required pattern on the photosensitive resin film obtained above, the film is exposed to i-line actinic radiation through a mask. The light source used for irradiation can be a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like, and in some cases, X-rays or electron beams can also be used.

[0131] The exposure dose varies depending on the type and amount of each component of the composition and the thickness of the dried film, but when using a high-pressure mercury lamp, it is 500 mJ / cm 2 (365nm sensor) or less. Through this stage, pixel size can be finely adjusted, enabling high resolution.

[0132] (3) Development stage As a development method, following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form a pattern. Through this step, a profile can be formed, achieving high resolution, ensuring color uniformity and improving clarity.

[0133] Yet another embodiment provides a display device including the photosensitive resin film.

[0134] The display device may be a micro organic light emitting diode (OLED) display device.

[0135] The micro organic light emitting device (OLED) display device includes an OLED substrate deposited on a silicon wafer and a color filter layer positioned on the OLED substrate for converting white light generated from the OLED substrate into a plurality of color lights, the color filter layer including red, green, and blue color filters. The photosensitive resin film, i.e., a microlens array, is positioned on the OLED substrate and the color filter layer. That is, the microlens array may surround the color filter layer on the OLED substrate.

[0136] For example, the micro organic light emitting device (OLED) display device may include an OLED substrate deposited on a silicon wafer, an inorganic layer stacked on the OLED substrate, and a color filter layer stacked on the inorganic layer to convert white light generated from the OLED substrate into a plurality of color lights, the color filter layer including a red color filter, a green color filter, and a blue color filter. The photosensitive resin film, i.e., the microlens array, is located on the inorganic layer and the color filter layer. That is, the microlens array may surround the color filter layer on the inorganic layer.

[0137] For example, the micro organic light emitting device (OLED) display device may include an OLED substrate deposited on a silicon wafer, an inorganic layer stacked on the OLED substrate, an adhesive protective layer stacked on the inorganic layer, and a color filter layer stacked on the adhesive protective layer to convert white light generated from the OLED substrate into a plurality of color lights, the color filter layer including a red color filter, a green color filter, and a blue color filter. The photosensitive resin film, i.e., a microlens array, is located on the adhesive protective layer and the color filter layer. That is, the microlens array may surround the color filter layer on the adhesive protective layer.

[0138] While conventional OLED substrates have been used, in which OLEDs are deposited on glass or polyimide substrates, the micro OLED display device according to one embodiment has OLEDs deposited on a silicon wafer, which is more advantageous for realizing a micro display. Such micro displays are attracting attention as next-generation displays and are expected to be applied to devices such as mixed reality (MR). In fact, Apple, Meta, and LG Display are all either already entering or planning to enter the next-generation MR device market.

[0139] The micro OLED display device with the above structure has WOLED (White OLED) deposited on a highly integrated silicon wafer, driven in pixel units, and is advantageous in ensuring high color reproduction and high resolution since it is easy to control the transmission wavelength through the color filter layer patterned with a resolution of 3μm or less.

[0140] For example, the thickness of the adhesive protective layer may be 1 μm or less, which can maximize the above-mentioned effects, i.e., improved adhesive strength to the color filter and improved residue characteristics.

[0141] For example, the color filter layer may have a thickness of 1.1 μm to 1.6 μm.

[0142] When the thickness of the color filter layer is controlled as described above, it is more advantageous to realize a micro OLED display device.

[0143] For example, the thickness of the inorganic layer may be 2 μm or less. Even in WOLEDs, light does not always diffuse only in the direction perpendicular to the OLED substrate, so red, green, and blue color mixing inevitably occurs. Therefore, in the past, an inorganic layer was deposited on the OLED substrate to prevent this color mixing. However, since color mixing cannot be completely prevented even by depositing an inorganic layer, in one embodiment, the inorganic layer is made thinner, for example, the thickness of the inorganic layer is controlled to 2 μm or less, thereby preventing minute light leakage.

[0144] As a result, the photosensitive resin composition according to one embodiment can produce a cured film by only low-temperature (100°C) curing during pre-baking and i-line photocuring, as described above, and therefore has a significant difference in achievable resolution compared to conventional display devices.

[0145] Preferred examples of the present invention will be described below, but the following examples are merely preferred embodiments of the present invention and the present invention is not limited to these examples. [Example]

[0146] (Production of polymer resins) Production Example 1: Synthesis of substance represented by chemical formula 5

[0147] [ka] Reaction Scheme 1

[0148] Compound 1a (10.0 mmol) was added to 30.0 mL of DMF (N,N-dimethylformamide) together with compound 1b (4.00 mmol) and potassium carbonate (K2CO3, 4.00 mmol), and the mixture was refluxed overnight. After confirming the consumption of compound 1a using thin-layer chromatography, the reaction mixture was added to distilled water to produce a precipitate. The substance was separated by vacuum filtration, washed with distilled water, and recrystallized using toluene to obtain compound 1c.

[0149] [ka] Reaction Scheme 2

[0150] Compound 1c (5.00 mmol) was added to 20.0 mL of 1,4-dioxane / H2O (v / v = 1 / 1) along with compound 1d (50.0 mmol) and potassium carbonate (K2CO3, 25.0 mmol) and stirred overnight at room temperature. After confirming the consumption of compound 1c using thin-layer chromatography, the reaction mixture was added to distilled water to produce a precipitate. The precipitate was separated by vacuum filtration, washed with distilled water, and dried overnight in a vacuum oven. Compound 1e was obtained by recrystallization using toluene.

[0151] [ka] Reaction Scheme 3

[0152] Compound 1e (10.0 mmol) was added to 30.0 mL of toluene together with acrylic acid (30.0 mmol), tetrabutylphosphonium bromide (TBPB, 1.00 mmol), and butylated hydroxytoluene (BHT, 0.50 mmol) and refluxed overnight. After removing the solvent under reduced pressure, the mixture was purified using column chromatography (eluent: n-hexane / EtOAc) to obtain compound 1f.

[0153] [ka] Reaction Scheme 4

[0154] Compound 1f (10.0 mmol) was added to 30.0 mL of cyclohexanone together with compound 1g (11.0 mmol), BHT (butylated hydroxytoluene, 0.5 wt%), and DBU (0.50 mmol). The reaction mixture was heated to 110°C and stirred for 6 hours to produce a polymer resin (weight average molecular weight: 4,900 g / mol) containing the repeating structural unit represented by Formula 5. The refractive index at 550 nm was 1.69.

[0155] Production Example 2: Synthesis of substance represented by chemical formula 6

[0156] [ka] Reaction Scheme 5

[0157] Compound 1a (10.0 mmol) was added to 1.50 mL of acetic acid, and excess 30% aqueous hydrogen peroxide was added at room temperature. The reaction mixture was stirred overnight at 120°C and then extracted with DCM (dichloromethane). The organic layer was passed through MgSO4, the solvent was removed under reduced pressure, and the compound 2a was obtained by purifying the organic layer using column chromatography (eluent: DCM / n-hexane).

[0158] [ka] Reaction Scheme 6

[0159] Compound 2b was synthesized in the same manner as in the synthesis of Compound 1c, except that Compound 2a was used instead of Compound 1a.

[0160] [ka] Reaction Scheme 7

[0161] Compound 2c was synthesized in the same manner as in the synthesis of Compound 1e, except that Compound 2b was used instead of Compound 1c.

[0162] [ka] Reaction Equation 8

[0163] Compound 2d was synthesized in the same manner as in the synthesis of Compound 1f, except that Compound 2c was used instead of Compound 1e.

[0164] [ka] Reaction Scheme 9

[0165] A polymer resin (weight average molecular weight: 4,600 g / mol) containing a repeating structural unit represented by Formula 6 was prepared in the same manner as in the synthesis of the material corresponding to Formula 5, except that Compound 2d was used instead of Compound 1f. The refractive index at 550 nm was 1.68.

[0166] Production Example 3: Synthesis of substance represented by chemical formula 7

[0167] [ka] Reaction Scheme 10

[0168] Compound 3a (10.0 mmol) and compound 1b (20.0 mmol) were dissolved in 40.0 mL of THF (tetrahydrofuran) at 0°C along with triethylamine (22.0 mmol) and stirred at room temperature for 2 hours. The solvent was removed under reduced pressure, and the reaction mixture dissolved in DCM (dichloromethane) was washed with 1N aqueous HCl, and the organic layer was passed through MgSO4. This was concentrated under reduced pressure to obtain compound 3b, which was used in the next reaction without further purification.

[0169] [ka] Reaction Scheme 11

[0170] Compound 3c was synthesized in the same manner as in the synthesis of Compound 1e, except that Compound 3b was used instead of Compound 1c.

[0171] [ka] Reaction 12

[0172] Compound 3d was synthesized in the same manner as in the synthesis of Compound 1f, except that Compound 3c was used instead of Compound 1e.

[0173] [ka] Reaction 13

[0174] A polymer resin (weight average molecular weight: 4,300 g / mol) containing a repeating structural unit represented by Formula 7 was prepared in the same manner as in the synthesis of the material corresponding to Formula 5, except that Compound 3d was used instead of Compound 1f. The refractive index at 550 nm was 1.66.

[0175] Production Example 4: Synthesis of substance represented by chemical formula 8

[0176] [ka] Reaction Scheme 14

[0177] Compound 4b was synthesized in the same manner as in the synthesis of compound 1e, except that compound 4a was used instead of compound 1c.

[0178] [ka] Reaction Scheme 15

[0179] Compound 4c was synthesized in the same manner as in the synthesis of Compound 1f, except that Compound 4b was used instead of Compound 1e.

[0180] [ka] Reaction Scheme 16

[0181] A polymer resin (weight average molecular weight: 5,100 g / mol) containing a repeating structural unit represented by Formula 8 was prepared in the same manner as in the synthesis of the material corresponding to Formula 5, except that Compound 4c was used instead of Compound 1f. The refractive index at 550 nm was 1.67.

[0182] Comparative Production Example 1: Synthesis of substance represented by chemical formula C-1

[0183] [ka] Reaction Scheme 17

[0184] A solution of compound 5a (25.0 mmol) and potassium tert-butoxide (KOt-Bu, 25.0 mmol) in 25.0 mL of DMF (N,N-dimethylformamide) was stirred at room temperature for 1 hour. Then, compound 1a (10.0 mmol) was added, and the temperature was raised to 120°C and stirred for 12 hours. After confirming the consumption of compound 1a using thin-layer chromatography, the reaction mixture was added to distilled water to produce a precipitate. The substance was separated by vacuum filtration, washed with distilled water, and recrystallized using toluene to obtain compound 5b.

[0185] [ka] Reaction Scheme 18

[0186] The compound 5b (5.00 mmol) was dissolved in 30.0 mL of THF (tetrahydrofuran), and N,N-dimethylaniline (15.0 mmol) was added thereto. After the solution was cooled to 0°C, a solution of the compound 5c (20.0 mmol) in 10.0 mL of THF was slowly added thereto. The reaction mixture was stirred overnight at room temperature, and then saturated aqueous sodium bicarbonate solution was added thereto. The solution was diluted with distilled water and extracted with chloroform. The organic layer was passed through MgSO4, concentrated under reduced pressure, and purified by column chromatography (developing solvent: DCM / n-hexane) to obtain the compound 5d.

[0187] [ka] Reaction Scheme 19

[0188] Compound 5d (3.00 mmol) was stirred with diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide (1.5 wt%) at 60°C for 20 minutes, and then irradiated with UV light using a Miksa mercury lamp (Model M-1S) for 30 minutes to prepare a polymer resin (weight average molecular weight: 14,500 g / mol) containing the repeating structural unit represented by formula C-1. The refractive index at 550 nm was 1.65.

[0189] Comparative Production Example 2: Synthesis of substance represented by chemical formula C-2

[0190] [ka] Reaction Scheme 20

[0191] The monomolecular compound represented by formula C-2 was prepared in the same manner as in the synthesis of compound 5d, except that compound 1c was used instead of compound 5b. The refractive index at 550 nm was 1.66.

[0192] (Production of Photosensitive Resin Composition) Examples 1 to 4, Comparative Examples 1 and 2 A photopolymerization initiator was dissolved in a solvent according to the composition shown in Table 1 below, and then stirred at room temperature for 2 hours. A polymer resin and a photopolymerizable monomer were added thereto, and the mixture was stirred at room temperature (25°C) for 1 hour, and then the entire solution was stirred again for 2 hours. The solution was filtered three times with a 0.45 μm filter to remove impurities, and a photosensitive resin composition was prepared.

[0193] [Table 1]

[0194] (A) Polymer resin (monomolecular compound) (A-1) Polymer resin of Production Example 1 (A-2) Polymer resin of Production Example 2 (A-3) Polymer resin of Production Example 3 (A-4) Polymer resin of Production Example 4 (A-5) Polymer resin of Comparative Production Example 1 (A-6) Monomolecular Compound of Comparative Production Example 2 (B) Photopolymerizable monomer Ethoxylated bisphenylfluorene diacrylate (BPF-022L, Hanno Chemical Co., Ltd.) (C) Photopolymerization initiator Oxime initiator (SPI-03, manufactured by Sanyosha) (D) Solvent Oxidant Propylene glycol monomethyl ether acetate (PGMEA, Daicel)

[0195] evaluation After confirming that the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were all transparent, their refractive indices at 550 nm were measured. Each was then coated onto an 8-inch silicon wafer using a SEMES K-SPIN at a rpm that would produce similar thicknesses. The wafers were then soft-baked at 100°C on a hot plate, and patterned using a Nikon i-line stepper under exposure conditions of (Dose: 200 ms / Focus: -0.3). After measuring the thickness using a TENCOR during the exposure process, the wafers were developed to reveal the pattern. EHD-100S solution (TMAH) was used as the developer, and the time (seconds) until the pattern appeared (BP) was measured.

[0196] The completed pattern on the patterned substrate after development was examined using a Hitachi CD-SEM to check the sensitivity of the pattern and the residue around the pattern. The pattern was confirmed to be a 96 μm intaglio pattern, and large-area residue was confirmed using an Olympus optical microscope, the results of which are shown in Table 2 below. The evaluation criteria for developability and pattern linearity are shown in Table 3 below.

[0197] [Table 2]

[0198] [Table 3]

[0199] Through the above evaluation, it can be seen that the photosensitive resin composition according to one embodiment is a transparent photosensitive resin composition, and has excellent pattern linearity and residue characteristics even when cured at low temperature, and is therefore suitable for use in microlenses surrounding color filters in micro OLEDs.

[0200] The present invention is not limited to the above-described embodiments, and can be manufactured in various different forms, and a person skilled in the art will understand that the present invention can be embodied in other specific forms without changing the technical concept or essential features of the present invention. Therefore, the above-described embodiments should be understood to be illustrative in all respects and not restrictive.

Claims

1. (A) a polymer resin having a refractive index of 1.66 or more; (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a solvent, The polymer resin has a repeating structural unit, The structural unit comprises a residue derived from an acid dianhydride.

2. The photosensitive resin composition according to claim 1 , wherein the structural unit further comprises a residue containing one or more sulfur atoms.

3. The photosensitive resin composition according to claim 2, wherein the residue containing one or more sulfur atoms includes a structure represented by the following Chemical Formulas 1 to 3: 【Chemistry 1】 Chemical formula 1 【Chemistry 2】 chemical formula 2 【Transformation 3】 chemical formula 3 In the above Chemical Formulas 1 to 3, X is ＊ -S- ＊ or ＊ -S(=O) ２ - ＊ and R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L １ ~L ６ are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

4. The photosensitive resin composition according to claim 2, wherein the residue containing one or more sulfur atoms comprises at least one structure selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2, Chemical Formula 2-1, and Chemical Formula 3-1: 【Chemistry 4】 Chemical formula 1-1 【Transformation 5】 Chemical formula 1-2 【Transformation 6】 Chemical formula 2-1 【Transformation 7】 Chemical formula 3-1

5. The photosensitive resin composition according to claim 1, wherein the residue derived from the acid dianhydride includes a structure represented by the following Chemical Formula 4-1 or Chemical Formula 4-2: 【Transformation 8】 Chemical formula 4-1 【Chemistry 9】 Chemical formula 4-2 In Chemical Formula 4-1 and Chemical Formula 4-2, Y is a single bond or ＊ -C(=O)- ＊ is.

6. 2. The photosensitive resin composition according to claim 1, wherein the repeating structural unit in the polymer resin is represented by any one of the following formulas 5 to 8: 【Chemistry 10】 chemical formula 5 【Chemistry 11】 chemical formula 6 【Chemistry 12】 chemical formula 7 【Chemistry 13】 Chemical formula 8

7. 2. The photosensitive resin composition according to claim 1, wherein the polymer resin is contained in an amount of 10 to 30% by weight based on the total amount of the photosensitive resin composition.

8. 2. The photosensitive resin composition according to claim 1, wherein the polymer resin has a weight average molecular weight of 20,000 g / mol to 80,000 g / mol.

9. The photosensitive resin composition contains 10% by weight to 30% by weight of the (A) polymer resin; 3% by weight to 15% by weight of the (B) photopolymerizable monomer, 0.1% by weight to 5% by weight of the (C) photopolymerization initiator, and The photosensitive resin composition according to claim 1 , further comprising the (D) residual solvent.

10. The photosensitive resin composition according to claim 1, further comprising an additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a polymerization inhibitor, and combinations thereof.

11. The photosensitive resin composition according to claim 1 , wherein the photosensitive resin composition has a refractive index of 1.62 or greater.

12. A photosensitive resin film produced using the photosensitive resin composition according to any one of claims 1 to 11.

13. A display device comprising the photosensitive resin film according to claim 12.

14. The display device includes an OLED substrate deposited on a silicon wafer, and a color filter layer positioned on the OLED substrate to convert white light generated from the OLED substrate into a plurality of color lights; The photosensitive resin film according to claim 12 is located on the OLED substrate and the color filter layer; 14. The display device of claim 13, wherein the color filter layer includes a red color filter, a green color filter, and a blue color filter.

15. A step of applying the photosensitive resin composition according to any one of claims 1 to 11; After the coating, pre-baking at a temperature of 100° C. or less; After the pre-baking, exposing the resist to i-line light; and developing the photosensitive resin film.

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