Photosensitive resin composition, photosensitive resin layer, method for manufacturing photosensitive resin layer, and display device

Abstract

Provided are a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, a display device including the photosensitive resin layer, and a method of manufacturing the photosensitive resin layer, the photosensitive resin composition including (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a solvent.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0065467 filed on May 20, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the same, a display device, and a manufacturing method of a photosensitive resin layer. BACKGROUND

[0004] Recently, interest in self-emissive (emissive type) micro organic light emitting diode (OLED) display panels applied to virtual reality (VR) devices, augmented reality (AR) devices, and mixed reality (MR) devices is increasing.

[0005] In a micro OLED display panel in which the pixel size is 10 times smaller than that of a general OLED display panel, it is difficult to form red (R) / green (G) / blue (B) light emitting layers using a conventional fine metal mask (FMM) technique. In other words, if a conventional liquid crystal display is applied to a VR, AR, or the like device, the color filter can have a pattern size that is too large to improve the resolution.

[0006] Accordingly, recently, OLED on Silicon (OLEDos) technology is being introduced to achieve a high resolution of about 4000 pixels per inch (ppi) or more. The corresponding technology uses an OLED deposited on a silicon wafer as a backlight to pattern a color filter thereon. Although the color filter used in a conventional liquid crystal display uses a pattern of about 100 µm on glass and is cured by exposure and post-baking at a high temperature of about 230 °C or higher, the color filter on the OLEDos must be cured at a low temperature because the high-temperature process cannot be performed due to the OLED. In addition, there is a problem that the light emitted from the OLED is inefficient when emitted outward. Accordingly, research on a high refractive index material that is transparent and can be sufficiently cured even at a low temperature is continuously ongoing. SUMMARY

[0007] Some example embodiments provide a photosensitive resin composition that is transparent and has a high refractive index and can be sufficiently cured even at a low temperature.

[0008] Some example embodiments provide a photosensitive resin layer manufactured using the photosensitive resin composition.

[0009] Some example embodiments provide a display device including the photosensitive resin layer.

[0010] Some example embodiments provide a method of manufacturing the photosensitive resin layer.

[0011] Some example embodiments provide a photosensitive resin composition including (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a solvent, wherein the photopolymerizable monomer is represented by Chemical Formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] In Chemical Formula 1,

[0015] R 1 and R 2 each independently is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl,

[0016] R 3 and R 4 each independently is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl,

[0017] L 1 and L 2 each independently is a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, or a substituted or unsubstituted C6 to C20 arylene,

[0018] L 3 to L 6 each independently is a substituted or unsubstituted C1 to C20 alkylene, and

[0019] m and n each independently are an integer of 0 to 4.

[0020] L 1 and L 2 each independently can be an unsubstituted C6 to C20 arylene.

[0021] L 1 and L 2 each independently can be a C6 to C20 arylene substituted with "a C1 to C20 alkyl substituted with a halogen group and / or a halogen group".

[0022] L 1 and L 2each independently can be unsubstituted C1to C20alkylene.

[0023] L 1 and L 2 each independently can be unsubstituted C3to C20cycloalkylene.

[0024] L 3 to L 6 may all be the same.

[0025] The photopolymerizable monomer can be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-7.

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 1-2]

[0029]

[0030] [Chemical Formula 1-3]

[0031]

[0032] [Chemical Formula 1-4]

[0033]

[0034] [Chemical Formula 1-5]

[0035]

[0036] [Chemical Formula 1-6]

[0037]

[0038] [Chemical Formula 1-7]

[0039]

[0040] The photosensitive resin composition can include about 10 to about 30 weight percent of (A) the binder resin; about 3 to about 15 weight percent of (B) the photopolymerizable monomer; about 0.1 to about 5 weight percent of (C) the photopolymerization initiator; and a balance of (D) the solvent, based on the total amount of the photosensitive resin composition.

[0041] The photosensitive resin composition can further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a polymerization inhibitor, or a combination thereof.

[0042] The photosensitive resin composition can have a refractive index greater than or equal to about 1.62 at 550 nanometers.

[0043] The photosensitive resin composition can have a transmittance greater than or equal to about 90% at 400 nm to 700 nm.

[0044] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0045] The photosensitive resin layer can be transparent.

[0046] Another embodiment provides a display device including the photosensitive resin layer.

[0047] The display device can be a micro-OLED display device including an OLED substrate on a silicon wafer and a color filter layer on the OLED substrate and converting white light generated by the OLED substrate into light of a plurality of colors, wherein the photosensitive resin layer is 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.

[0048] Some example embodiments provide a method of manufacturing a photosensitive resin layer, including coating a photosensitive resin composition; pre-baking at a temperature of about 100°C or less after coating; exposing to i-line after pre-baking; and developing.

[0049] Other embodiments are included in the following detailed description.

[0050] The photosensitive resin composition according to some example embodiments is a transparent photosensitive resin composition that can be cured at a low temperature of 100°C or less, has a high refractive index at 550 nm, has a high transmittance in a visible light range (400 nm to 700 nm), and can achieve the above effects only through photocuring (i-line exposure) at a pre-baking temperature of 100°C or less, and thus can be appropriately applied as a microlens layer (microlens array) in a micro-OLED display device capable of achieving a fine pattern. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 is a schematic diagram showing the structure of a micro-OLED display device according to some example embodiments. DETAILED DESCRIPTION

[0052] Hereinafter, the embodiments will be described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

[0053] In the present text, when a specific definition is not provided otherwise, "alkyl" means C1 to C20 alkyl, "alkenyl" means C2 to C20 alkenyl, "cycloalkenyl" means C3 to C20 cycloalkenyl, "heterocycloalkenyl" means C3 to C20 heterocycloalkenyl, "aryl" means C6 to C20 aryl, "aralkyl" means C6 to C20 aralkyl, "alkylene" means C1 to C20 alkylene, "arylene" means C6 to C20 arylene, "alkylarylene" means C6 to C20 alkylarylene, "heteroarylene" means C3 to C20 heteroarylene, "alkyloxy" means C1 to C20 alkyloxy.

[0054] In the present text, when a specific definition is not provided otherwise, "substituted" means that at least one hydrogen of the compound is replaced with a substituent selected from the group consisting of a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azido group, an amido group, a hydrazino group, a hydrazon group, a carbonyl group, a carboxamide group, a mercapto 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 or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group or a combination thereof.

[0055] In the present text, when a specific definition is not provided otherwise, "hetero" means a heteroatom including at least one of N, O, S and P in a chemical formula.

[0056] In the present text, when a specific definition is not provided otherwise, "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid".

[0057] In the present text, when a definition is not provided otherwise, the term "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymer.

[0058] In the chemical formulae of the present specification, unless a specific definition is provided otherwise, when a position at which a chemical bond should be given is not drawn with a chemical bond, hydrogen is bonded at the position.

[0059] In the present text, when a definition is not provided otherwise, "*" means a connecting moiety between the same or different atoms or chemical formulae.

[0060] A photosensitive resin composition according to some example embodiments includes (A) a binder resin; (B) a photopolymerizable monomer represented by Chemical Formula 1; (C) a photopolymerization initiator; and (D) a solvent.

[0061] [Chemical Formula 1]

[0062]

[0063] In Chemical Formula 1,

[0064] R 1 and R 2 each independently is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0065] R 3 and R 4 each independently is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0066] L 1 and L 2 each independently is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,

[0067] L 3 to L 6 each independently is a substituted or unsubstituted C1 to C20 alkylene group, and

[0068] m and n each independently are an integer of 0 to 4.

[0069] Among many types of display devices, liquid crystal display devices have advantages of lightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely applied to notebook computers, monitors, and television screens. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, and an upper substrate on which an active circuit portion including a liquid crystal layer, a thin film transistor, and a capacitor layer, and an ITO pixel electrode are formed. The color filter forms each pixel in a pixel region by sequentially stacking a plurality of color filters (typically formed of a plurality of colors (generally, red (R), green (G), and blue (B) three primary colors)) in a predetermined order, and the black matrix layer is provided on a transparent substrate in a predetermined pattern to form a boundary between pixels. The pigment dispersion method is one of methods of forming a color filter, which provides a colored thin film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate including a black matrix, performing light irradiation on the formed pattern, removing an unexposed portion with a solvent, and thermally curing the same. A color photosensitive resin composition for manufacturing a color filter according to the pigment dispersion method generally includes an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives, etc. The pigment dispersion method having the above-described characteristics is actively applied to the manufacture of LCDs such as mobile phones, notebook computers, monitors, and televisions.

[0070] However, when the technology of manufacturing a color filter for a liquid crystal display is applied to a virtual reality (VR) and an augmented reality (AR) device, which have recently been attracting much attention in the market, there is a limitation in resolution. In order to achieve a high resolution of greater than or equal to about 4000 ppi, a silicon on OLED (OLEDoS) technology, which is a technology of using an OLED deposited on a silicon wafer as a backlight and forming a color filter pattern thereon, is being introduced. Although a conventional color filter for a liquid crystal display is cured through a post-baking process at a high temperature of greater than or equal to about 230°C, a color filter mounted on an OLEDoS must be curable at a low temperature due to the durability of the OLED material. In addition, micropatterning is essential to achieve the required resolution within the small size of the VR and AR devices. Such a technology that is only possible to be cured at a low temperature (about 100°C) can have a potential problem of color change due to low chemical resistance. In order to improve this problem, it is essential to increase the hardness of the photoresist.

[0071] A display device like an OLED generally has a problem of low efficiency caused by light leakage generated thereby. As a solution to this problem, a technology of using a high refractive index layer or a high refractive index pattern to control a refractive index difference, which is one of the causes of light loss at the time of light leakage, is known.

[0072] As an attempt to highly functionalize a polymer compound, a polyimide-based polymer material containing a sulfur atom has been mainly developed to secure a high refractive index (>1.60). However, the polyimide-based material has a characteristic of absorbing light in a wavelength range of about 400 nanometers, and thus is not suitable for a microlens that receives light in a visible light region (about 400 nanometers to about 700 nanometers).

[0073] The present application does not relate to a conventional color photoresist for manufacturing a color filter, but relates to a microlens applied to a micro OLED display device, in which the microlens maintains a high refractive index of greater than or equal to about 1.62, such as greater than or equal to about 1.63, such as greater than or equal to about 1.64, such as greater than or equal to about 1.65, or such as greater than or equal to about 1.66, at 550 nanometers, but still has a high transmittance of greater than or equal to about 90%, or such as greater than or equal to about 95%, in a visible light region, and thus can be very suitable for receiving light.

[0074] Hereinafter, each component is described in detail.

[0075] (A) Binder Resin

[0076] The binder resin can include an acrylic binder resin.

[0077] The acrylic adhesive resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerized therewith, and is a resin including one or more acrylic repeat units.

[0078] The first ethylenically unsaturated monomer can be an ethylenically unsaturated monomer including at least one carboxyl group, specific examples of which include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0079] The first ethylenically unsaturated monomer can be included in an amount of 5 to 50 wt% (e.g., in an amount of 10 to 40 wt%) based on the total amount of the acrylic adhesive resin.

[0080] Examples of the second ethylenically unsaturated monomer can include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, and the like; unsaturated carboxylic acid ester compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxy butyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl(meth)acrylate, and the like; unsaturated aminoalkyl carboxylic acid ester compounds such as 2-aminoethyl(meth)acrylate and 2-dimethylaminoethyl(meth)acrylate, and the like; vinyl carboxylate compounds such as vinyl acetate and vinyl benzoate, and the like; unsaturated glycidyl carboxylic acid ester compounds such as glycidyl(meth)acrylate, and the like; cyano ethylene compounds such as (meth)acrylonitrile, and the like; unsaturated amide compounds such as (meth)acrylamide, and the like, and the compounds can be used alone or in the form of a mixture of two or more.

[0081] Specific examples of the acrylic adhesive resin can be (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, but are not limited thereto, and can be used alone or as a mixture of two or more.

[0082] The acrylic adhesive resin can have a weight average molecular weight of about 3,000 g / mol to about 20,000 g / mol and a double bond equivalent of greater than or equal to about 340 g / mol. If the weight average molecular weight and the double bond equivalent of the acrylic adhesive resin are within the above ranges, it has excellent pattern forming properties, and the manufactured film can have excellent mechanical and thermal properties.

[0083] The binder resin can include an epoxy-based binder resin.

[0084] The binder resin can improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin can be, for example, a phenol novolac epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is not limited thereto.

[0085] Further, the binder resin including the epoxy-based binder resin ensures dispersion stability of a colorant such as a pigment, which will be described later, and helps to form a pixel having a desired resolution in a development process.

[0086] The epoxy-based binder resin can be included in an amount of about 1 wt% to about 10 wt% (for example, about 5 wt% to about 10 wt%) based on the total amount of the binder resin. If the epoxy-based binder resin is included in the above range, film residue rate and chemical resistance can be greatly improved.

[0087] The epoxy equivalent weight of the epoxy-based resin can be about 150 g / eq to about 200 g / eq. If the epoxy-based binder resin having an epoxy equivalent weight in the above range is included in the binder resin, it has an advantageous effect in improving the degree of curing of the formed pattern and fixing the colorant in the pattern-formed structure.

[0088] Further, the binder resin can be included in an amount of about 10 wt% to about 30 wt% (for example, about 10 wt% to about 25 wt%) based on the total amount of the photosensitive resin composition. If the above binder resin is included in the above range, excellent sensitivity, developability, resolution, and linearity of a pattern can be obtained.

[0089] (B) a photopolymerizable monomer

[0090] According to some example embodiments, the photopolymerizable monomer in the photosensitive resin composition can be a single compound or a mixture of two different types of compounds.

[0091] For example, the photopolymerizable monomer can be a tri-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond, and specifically, the photopolymerizable monomer can be represented by Chemical Formula 1.

[0092] Since the photopolymerizable monomer is represented by Chemical Formula 1, it can form a pattern having excellent heat resistance, light resistance, and chemical resistance by sufficient polymerization at the time of exposure in a pattern forming process, and can also have a high refractive index at 550 nm and a high transmittance in the visible light region.

[0093] For example, L1 and L 2 may each independently be an unsubstituted C6 to C20 arylene group, for example L 1 and L 2 may each independently be an unsubstituted C6 arylene group (e.g., phenylene group) or an unsubstituted C10 arylene group (e.g., naphthylene group).

[0094] for example, L 1 and L 2 may each independently be a C6 to C20 arylene group substituted with a "halogen group and / or a C1 to C20 alkyl group substituted with a halogen group".

[0095] The halogen group can be a fluoro group, a chloro group, a bromo group, or an iodo group, and the C1 to C20 alkyl group substituted with a halogen group can be, for example, a trifluoromethyl group.

[0096] for example, L 1 and L 2 may each independently be an unsubstituted C1 to C20 alkylene group, for example, an unsubstituted C1 to C10 alkylene group.

[0097] for example, L 1 and L 2 may each independently be an unsubstituted C3 to C20 cycloalkylene group, for example, an unsubstituted C6 cycloalkylene group, for example, a cyclohexylene group.

[0098] for example, L 3 to L 6 may all be the same, for example, L 3 to L 6 may all be a methylene group or an ethylene group.

[0099] For example, the photopolymerizable monomer can be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-7, but is not necessarily limited thereto.

[0100] [Chemical Formula 1-1]

[0101]

[0102] [Chemical Formula 1-2]

[0103]

[0104] [Chemical Formula 1-3]

[0105]

[0106] [Chemical Formula 1-4]

[0107]

[0108] [Chemical Formula 1-5]

[0109]

[0110] [Chemical Formula 1-6]

[0111]

[0112] [Chemical Formula 1-7]

[0113]

[0114] The photosensitive resin composition according to some example embodiments can further include a photopolymerizable monomer having a different structure from the photopolymerizable monomer represented by Chemical Formula 1.

[0115] Specific examples of the photopolymerizable monomer having a different structure from Chemical Formula 1 can be 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, 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, phenol novolac epoxy (meth)acrylate, ethoxylated diphenylfluorene diacrylate, ethoxylated naphthalene-based diacrylate, ethoxylated sulfur-based diacrylate, etc.

[0116] Commercially available examples of the photopolymerizable monomer having a different structure from Chemical Formula 1 are as follows. Examples of the mono-functional (meth)acrylic ester can include Aronix (East Asia Synthesis Chemical Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.); (Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the di-functional (meth)acrylic ester can include Aronix (East Asia Synthesis Chemical Industry Co., Ltd.), KAYARAD (Nippon Kayaku Co., Ltd.), BPF-022, BPF-022B, BPF-022L, BPF-022G, BPF-102, BPF-152, BPF-202, BPF-302, BN-042, BN-102, TBP-042, TBP-102 (Hanhwa Chemical Corporation, etc.). Examples of the tri-functional (meth)acrylic acid ester can include Anix KAYARAD (Nippon Shokubai Co., Ltd.), IRGACURE KAYARAD (Nippon Shokubai Co., Ltd.), BPF-022, BPF-022B, BPF-022L, BPF-022G, BPF-102, BPF-152, BPF-202, BPF-302, BN-042, BN-102, TBP-042, TBP-102 (Hanhwa Chemical Corporation, etc.). These can be used alone or as a mixture of two or more.

[0117] The photopolymerizable monomer can be treated with an anhydride to improve developability.

[0118] For example, the photopolymerizable monomer can be included in an amount of about 3 wt% to about 15 wt% (e.g., about 5 wt% to about 10 wt%) based on the total amount of the photosensitive resin composition. For example, the photopolymerizable monomer can be included in an amount of about 20 wt% to about 60 wt% (e.g., about 30 wt% to about 50 wt%) based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerizable monomer is included within this range, the photopolymerizable monomer is sufficiently cured during exposure in a pattern forming process and has excellent reliability, and developability to an alkaline developer can be improved.

[0119] (C) Photopolymerization initiator

[0120] The photosensitive resin composition according to some embodiments includes a photopolymerization initiator. The photopolymerization initiator can include a phenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, etc.

[0121] Examples of the phenone compound can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0122] Examples of benzophenone compounds can be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0123] Examples of thioxanthone compounds can be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0124] Examples of benzoin compounds can be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, and the like.

[0125] Examples of triazine compounds can be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenethyl)-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, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-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.

[0126] Examples of oxime compounds can be O-acyl oxime 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. Specific examples of O-acyl oxime compounds can be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and the like.

[0127] In addition to the above-mentioned compounds, the photopolymerization initiator can be used together with, for example, a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a bisimidazole compound, or the like.

[0128] For example, the photopolymerization initiator can be included in an amount of about 0.1 wt% to about 5 wt% (for example, about 0.5 wt% to about 3 wt%) based on the total amount of the photosensitive resin composition. For example, the photopolymerization initiator can be included in an amount of about 1 wt% to about 5 wt% (for example, about 1.5 wt% to about 3 wt%) based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerization initiator is included within the above-mentioned range, the photopolymerization reaction sufficiently occurs during exposure in the pattern forming process of manufacturing the microlens, thereby resulting in excellent sensitivity and improved transmittance.

[0129] (D) Solvent

[0130] The solvent can be a material that is compatible with the polymer resin, the photopolymerization monomer, and the photopolymerization initiator but does not react.

[0131] Examples of the solvent can include: alcohols such as methanol, ethanol and the like; ethers such as dichloroethane, n-butyl ether, diisopentyl ether, methyl phenyl ether, tetrahydrofuran and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and the like; sulfolane acetates such as methyl sulfolane acetate, ethyl sulfolane acetate, diethyl sulfolane acetate and the like; 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, diethylene glycol diethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactate esters such as methyl lactate, ethyl lactate and the like; alkyl oxoacetates such as methyl oxoacetate, ethyl oxoacetate, butyl oxoacetate and the like; alkoxylated alkyl oxoacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; 3-oxopropionic acid alkyl esters such as 3-oxopropionic acid methyl ester, 3-oxopropionic acid ethyl ester and the like; 3-alkoxylated propionic acid alkyl esters such as 3-methoxylated propionic acid methyl ester, 3-methoxylated propionic acid ethyl ester, 3-ethoxylated propionic acid ethyl ester, 3-ethoxylated propionic acid methyl ester and the like; 2-oxopropionic acid alkyl esters such as 2-oxopropionic acid methyl ester, 2-oxopropionic acid ethyl ester, 2-oxopropionic acid propyl ester and the like; 2-alkoxylated propionic acid alkyl esters such as 2-methoxylated propionic acid methyl ester, 2-methoxylated propionic acid ethyl ester, 2-ethoxylated propionic acid ethyl ester, 2-ethoxylated propionic acid methyl ester and the like; 2-oxo-2-methylpropionic acid esters such as 2-oxo-2-methylpropionic acid methyl ester, 2-oxo-2-methylpropionic acid ethyl ester and the like; 2-alkoxylated-2-methylpropionic acid alkyl esters such as 2-methoxylated-2-methylpropionic acid methyl ester, 2-ethoxylated-2-methylpropionic acid ethyl ester and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methylethyl butyrate and the like; keto acid esters such as ethyl pyruvate and the like. In addition, 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, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl sulfolane acetate and the like can also be used.

[0132] In consideration of compatibility and reactivity, it is desirable that diol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, and the like; esters such as 2-hydroxyethyl propionate, and the like; carbitols such as diethylene glycol monomethyl ether, and the like; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like can be used.

[0133] The solvent can be included in a balance, for example, about 50 wt% to about 90 wt%, for example, about 60 wt% to about 80 wt%, for example, about 70 wt% to about 80 wt%, based on the total amount of the photosensitive resin composition. If the solvent is included in the range, the photosensitive resin composition can have an appropriate viscosity, thereby improving processability in producing a photosensitive resin layer, particularly, a microlens.

[0134] (E) Other additives

[0135] Meanwhile, the photosensitive resin composition can further include an additive such as malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a polymerization inhibitor, or a combination thereof.

[0136] The silane-based coupling agent can have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloyloxy group, an isocyanate group, or an epoxy group to improve adhesion to a substrate. However, if the silane-based coupling agent is used, since the photosensitive resin composition according to some embodiments is a colorant-free composition, that is, a transparent photosensitive resin composition, if the refractive index of the polymer resin at 550 nm is not controlled as described above, an effect of improving adhesion to a color filter can not be obtained.

[0137] Examples of the silane-based coupling agent can include trimethoxysilyl benzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. These can be used alone or two or more kinds can be used in mixture.

[0138] The silane-based coupling agent can be included in an amount of about 0.01 parts by weight to about 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. If the silane-based coupling agent is included in the above range, adhesion, storage capacity, and the like are improved.

[0139] Further, as necessary, the photosensitive resin composition can further include a surfactant such as a fluorine-based surfactant and / or a silicone-based surfactant to improve coating properties and prevent defects from being formed.

[0140] Examples of fluorinated surfactants can be commercial fluorinated surfactants, such as those from BM Chemie Inc. etc.; MEGAFACE F of Dai Nippon Ink & Chemical Co., Ltd. MEGAFACE F MEGAFACE F MEGAFACE F MEGAFACE F etc.; Sumitomo 3M Co., Ltd.’s FULORAD FULORAD FULORAD FULORAD etc.; SURFLON from Asahi Glass Co., Ltd. SURFLON SURFLON SURFLON SURFLON etc.; Toray Silicone Oil Co., Ltd. wait.

[0141] Silicone surfactants can be commercial silicone surfactants, such as BYK Chem's BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, and BYK-325.

[0142] The surfactant can be used in amounts from about 0.001 parts by weight to about 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. If the surfactant is included in this range, uniform coating can be ensured, stains can be avoided, and wetting on the IZO substrate or glass substrate can be improved.

[0143] Polymerization inhibitors may include, but are not limited to, catechol-based compounds. Since the photosensitive resin compositions according to some embodiments also include catechol-based compounds, room-temperature crosslinking can be prevented during exposure after coating the photosensitive resin composition.

[0144] For example, catechol compounds may include catechol, tert-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosoaniline-O,O')aluminum, but are not necessarily limited to these.

[0145] The catechol compound can be used in a dispersion form, and the polymerization inhibitor in a dispersion form can be included in an amount of about 0.001 wt% to about 3 wt% (for example, about 0.01 wt% to about 1 wt%) based on the total amount of the photosensitive resin composition. If the polymerization inhibitor is within the above range, the room temperature aging problem can be solved and the sensitivity decrease and surface peeling can be prevented.

[0146] In addition, unless the additive reduces the performance of the photosensitive resin composition, the photosensitive resin composition can include a predetermined amount of other additives (such as a stabilizer, etc.).

[0147] The photosensitive resin composition according to some embodiments can be positive or negative, but should be negative to completely remove the residue of the pattern exposed area after exposing and developing the composition having a light-shielding property.

[0148] On the other hand, the photosensitive resin composition according to some example embodiments including the photopolymerizable monomer represented by Chemical Formula 1 can have a refractive index greater than or equal to about 1.62 (at about 550 nm), for example, greater than or equal to about 1.62 and less than or equal to about 1.8 (at about 550 nm). In addition, the photosensitive resin composition according to some example embodiments including the photopolymerizable monomer represented by Chemical Formula 1 can have a transmittance greater than or equal to about 90% in the visible light region (about 400 nm to about 700 nm), for example, greater than or equal to about 95%, for example, greater than or equal to about 96%, or for example, greater than or equal to about 97%. The photosensitive resin composition including the photopolymerizable monomer represented by Chemical Formula 1, whose refractive index at about 550 nm and transmittance in the visible light region are controlled as described above, can significantly reduce light loss when white light generated from an OLED substrate leaks out, and further advantageously improve developability and fine patterning capability. Due to these characteristics, the photosensitive resin composition according to some example embodiments can be very suitable as a microlens material for OLEDoS.

[0149] Some embodiments provide a photosensitive resin layer manufactured by low-temperature curing, exposing, and developing the above-described photosensitive resin composition. The difference from the conventional liquid crystal display or semiconductor process is that a post-curing (post-baking) process is not required.

[0150] A method of manufacturing a photosensitive resin layer is as follows.

[0151] (1) Coating and film formation (low-temperature curing)

[0152] The photosensitive resin composition is coated on a substrate such as a silicon wafer subjected to a predetermined pretreatment to have a desired thickness using a spin or slit coating method, a roll coating method, a screen printing method, a coater method, or the like, and heated at 100°C for 1 to 10 minutes to remove the solvent, thereby forming a photosensitive resin layer. Through this step, it is possible to improve the image quality or the like.

[0153] (2) Exposure

[0154] After placing a mask forming a desired pattern on the obtained photosensitive resin layer, exposure is performed by irradiating photochemically active rays of i-line. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used, and in some cases, an X-ray, an electron beam, or the like can be used.

[0155] For example, when a high-pressure mercury lamp is used, the exposure process uses a light dose of 500 mJ / cm 2 or less (using a 365 nm sensor). However, the light dose can vary depending on the type of each component, the combination ratio, and the dry film thickness. Through this step, it is possible to finely adjust the pixel size, thereby achieving high resolution.

[0156] (3) Development

[0157] In the development method, after the exposure step, an unnecessary portion is dissolved and removed using an aqueous alkali solution as a developer, and only the exposed portion is left to form a pattern. Through this step, it is possible to form a profile to achieve high resolution, and it is possible to ensure color uniformity to improve the sharpness.

[0158] Some embodiments provide a display device including a photosensitive resin layer.

[0159] The display device can be a micro organic light emitting diode (OLED) display device.

[0160] The micro OLED display device can include an OLED substrate deposited on a silicon wafer and a color filter layer located on the OLED substrate and converting white light generated by the OLED substrate into light of a plurality of colors, wherein the color filter layer includes a red color filter, a green color filter, and a blue color filter. Also, the photosensitive resin layer (i.e., the microlens layer) is located on the OLED substrate and the color filter layer. That is, the microlens layer can surround the color filter layer on the OLED substrate.

[0161] For example, the micro OLED display device includes an OLED substrate deposited on a silicon wafer, an inorganic layer stacked on the OLED substrate, a color filter layer stacked on the inorganic layer and converting white light generated by the OLED substrate into light of a plurality of colors, and a photosensitive resin layer. The color filter layer can include a red color filter, a green color filter, and a blue color filter. The photosensitive resin layer (i.e., a microlens layer) is located on the inorganic layer and the color filter layer. That is, the microlens layer can surround the color filter layer on the inorganic layer.

[0162] For example, the micro OLED display device can include an OLED substrate deposited on a silicon wafer, an inorganic layer stacked on the OLED substrate, an adhesive protection layer stacked on the inorganic layer, and a color filter layer stacked on the adhesive protection layer and converting white light generated by the OLED substrate into light of a plurality of colors, wherein the color filter layer includes a red color filter, a green color filter, and a blue color filter. And a photosensitive resin layer (i.e., a microlens layer) is located on the adhesive protection layer and the color filter layer. That is, the microlens layer can surround the color filter layer on the adhesive protection layer.

[0163] Conventionally, an organic light emitting diode substrate in which an organic light emitting diode is deposited on a glass or polyimide substrate has been used, but the micro organic light emitting diode display device according to some embodiments can be more advantageous in implementing a micro display because the organic light emitting diode is deposited on a silicon wafer. These micro displays are attracting attention as next-generation displays, and it is expected that micro displays will be applied to devices such as MR. In fact, Apple, Meta, LG Display have all entered or announced entry into the next-generation MR device market.

[0164] The micro OLED display device having the above structure can be driven on a pixel basis by depositing a white organic light emitting diode (WOLED) on a highly integrated silicon wafer, and easily control the transmission wavelength through a patterned color filter layer having a resolution less than or equal to about 3 μm, thereby achieving high color reproduction and ensuring high resolution.

[0165] For example, the thickness of the adhesive protection layer can be less than or equal to 1 μm. In this case, the above effects (i.e., effects of improving adhesion to the color filter and improving residue characteristics) can be further maximized.

[0166] For example, the color filter layer can have a thickness of about 1.1 μm to about 1.6 μm.

[0167] If the thickness of the color filter layer is controlled in the above-described manner, it can be more advantageous to implement the micro OLED display device.

[0168] For example, the inorganic layer can have a thickness of less than or equal to about 2 μm. Even if a WOLED is used, light does not always diffuse in a direction perpendicular to the OLED substrate, and thus color mixing of red, green, and blue colors inevitably occurs. Accordingly, in the past, an inorganic layer was deposited on an OLED substrate to prevent such color mixing. However, since color mixing cannot be completely prevented even by depositing an inorganic layer, in some example embodiments, a subtle light leakage phenomenon can be prevented by thinning the inorganic layer, e.g., controlling the thickness of the inorganic layer to be less than or equal to about 2 μm.

[0169] Finally, the photosensitive resin composition according to some embodiments allows a cured layer to be produced only by low-temperature (100°C) curing during pre-baking and i-line photo-curing, as described above, and there is inevitably a great difference in achievable resolution compared to conventional display devices.

[0170] Preferred examples of the present application will be described below. However, the examples below are merely preferred examples of the present application, and the present application is not limited by the examples below.

[0171] (Examples)

[0172] Preparation Example 1: Synthesis of a compound represented by Chemical Formula 1

[0173] (Reaction Scheme 1)

[0174]

[0175] Compound 1a (10.0 mmol) was added to 30.0 mL of N,N-dimethylformamide (DMF) together with compound 1b (4.00 mmol) and potassium carbonate (K2CO3, 4.00 mmol), and the reaction was refluxed overnight. After confirming the depletion of compound 1a by thin layer chromatography, the reaction mixture was added to distilled water to form a precipitate. After isolating the substance by vacuum filtration, the substance was washed with distilled water and recrystallized using toluene to obtain compound 1c.

[0176] (Reaction Scheme 2)

[0177]

[0178] Compound 1c (5.00 mmol) was added to 20.0 mL of 1,4-dioxane / H2O (volume ratio = 1 / 1) with potassium carbonate (K2CO3, 25.0 mmol) and stirred at room temperature overnight. After confirming the consumption of compound 1c by thin layer chromatography, the reaction mixture was added to distilled water to form a precipitate. The substance was separated by pressure filtration, washed with distilled water, and dried in a vacuum oven overnight. Compound 1e was obtained using toluene recrystallization.

[0179] (Reaction Scheme 3)

[0180]

[0181] Compound 1e (10.0 mmol) was added to 30.0 mL of toluene with compound 1f (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, purification by column chromatography (eluent: n-hexane / ethyl acetate) obtained compound 1g.

[0182] (Reaction Scheme 4)

[0183]

[0184] Compound 1g (10.0 mmol) described above was added to 10.0 mL of tetrahydrofuran (THF) with compound 1h (20.5 mmol) and 4-dimethylaminopyridine (4-DMAP, 1.00 mmol) and refluxed overnight. After removing the solvent under reduced pressure, purification by column chromatography (eluent: dichloromethane / methanol) obtained a compound represented by Chemical Formula 1.

[0185] The analysis results of the compound represented by Chemical Formula 1 are as follows.

[0186] MALDI-TOF MS: 1017.13 m / z

[0187] Preparation Example 2: Synthesis of a compound represented by Chemical Formula 2

[0188] (Reaction Scheme 5)

[0189]

[0190] A compound represented by Chemical Formula 2 was synthesized in the same manner as the method of synthesizing a compound represented by Chemical Formula 1, except that compound 2a was used instead of compound 1h.

[0191] The analysis results of the compound represented by Chemical Formula 2 are as follows.

[0192] MALDI-TOF MS: 1153.10 m / z

[0193] Preparation Example 3: Synthesis of a compound represented by Chemical Formula 3

[0194] (Reaction Scheme 6)

[0195]

[0196] A compound represented by Chemical Formula 3 was synthesized in the same manner as the method of synthesizing a compound represented by Chemical Formula 1, except that compound 3a was used instead of compound 1h.

[0197] Analytical results of a compound represented by Chemical Formula 3 are as follows.

[0198] MALDI-TOF MS: 1117.16 m / z

[0199] Preparation Example 4: Synthesis of a compound represented by Chemical Formula 4

[0200] (Reaction Scheme 7)

[0201]

[0202] A compound 4b was synthesized in the same manner as the method of synthesizing compound 1g, except that compound 4a was used instead of compound 1f.

[0203] (Reaction Scheme 8)

[0204]

[0205] A compound represented by Chemical Formula 4 was synthesized in the same manner as the method of synthesizing a compound represented by Chemical Formula 1, except that compound 4c was used instead of compound 1h.

[0206] Analytical results of a compound represented by Chemical Formula 4 are as follows.

[0207] MALDI-TOF MS: 1117.12 m / z

[0208] Preparation Example 5: Synthesis of a compound represented by Chemical Formula 5

[0209] (Reaction Scheme 9)

[0210]

[0211] A compound 5b was synthesized in the same manner as the method of synthesizing compound 1c, except that compound 5a was used instead of compound 1b.

[0212] (Reaction Scheme 10)

[0213]

[0214] Compound 5c was synthesized in the same manner as the method for synthesizing Compound le except that Compound 5b was used instead of Compound lc.

[0215] (Reaction Scheme 11)

[0216]

[0217] Compound 5d was synthesized in the same manner as the method for synthesizing Compound lg except that Compound 5c was used instead of Compound le.

[0218] (Reaction Scheme 12)

[0219]

[0220] Compound 5 was synthesized in the same manner as the method for synthesizing the compound represented by Chemical Formula 1 except that Compound 5d was used instead of Compound lg.

[0221] The analytical results of the compound represented by Chemical Formula 5 are as follows.

[0222] MALDI-TOF MS: 1073.19 m / z

[0223] Preparation Example 6: Synthesis of a compound represented by Chemical Formula 6

[0224] (Reaction Scheme 13)

[0225]

[0226] Compound 6 was synthesized in the same manner as the method for synthesizing the compound represented by Chemical Formula 1 except that Compound 6a was used instead of Compound lh.

[0227] The analytical results of the compound represented by Chemical Formula 6 are as follows.

[0228] MALDI-TOF MS: 921.13 m / z

[0229] Preparation Example 7: Synthesis of a compound represented by Chemical Formula 7

[0230] (Reaction Scheme 14)

[0231]

[0232] Compound 7 was synthesized in the same manner as the method for synthesizing the compound represented by Chemical Formula 1 except that Compound 7a was used instead of Compound lh.

[0233] The analytical results of the compound represented by Chemical Formula 7 are as follows.

[0234] MALDI-TOF MS: 1029.22 m / z

[0235] Comparative Preparation Example 1: Synthesis of a compound represented by Chemical Formula C-1

[0236] (Reaction Scheme 15)

[0237]

[0238] A solution of compound 8a (25.0 mmol) and potassium tert-butoxide (KOt-Bu, 25.0 mmol) dissolved in 25.0 mL of N,N-dimethylformamide (DMF) was stirred at room temperature for 1 hour. Thereafter, compound 1a (10.0 mmol) was added, the temperature was raised to 120°C, and stirred for 12 hours. After confirming the consumption of compound 1a by thin layer chromatography, the reaction mixture was added to distilled water to produce a precipitate. After isolating the substance by vacuum filtration, the substance was washed with distilled water, and recrystallized using toluene to obtain compound 8b.

[0239] (Reaction Scheme 16)

[0240]

[0241] N,N-dimethylaniline (15.0 mmol) was added to compound 8b (5.00 mmol) dissolved in 30.0 mL of tetrahydrofuran (THF). After cooling the solution to 0°C, a solution of compound 8c (20.0 mmol) dissolved in 10.0 mL of THF was slowly added. The reaction mixture was stirred at room temperature overnight, and then saturated aqueous sodium bicarbonate solution was added. The solution was diluted with distilled water and extracted with chloroform. The organic layer was passed through MgSO4and concentrated under reduced pressure, and the resulting product was purified by column chromatography (eluent: DCM / n-hexane) to obtain a compound represented by Chemical Formula C-1.

[0242] The analytical results of the compound represented by Chemical Formula C-1 are as follows.

[0243] MALDI-TOF MS: 477.02 m / z

[0244] Comparative Preparation Example 2: Synthesis of a compound represented by Chemical Formula C-2

[0245] (Reaction Scheme 17)

[0246]

[0247] A compound represented by Chemical Formula C-2 was synthesized in the same manner as the compound represented by Chemical Formula C-1, except that Compound 1c was used instead of Compound 8b.

[0248] The results of the analysis of the compound represented by Chemical Formula C-2 were as follows.

[0249] MALDI-TOF MS: 573.02 m / z

[0250] (Preparation of photosensitive resin composition)

[0251] Examples 1 to 7 and Comparative Examples 1 and 2

[0252] The photopolymerization initiator was dissolved in the solvent and stirred at room temperature for 2 hours according to the composition shown in Table 1. During this process, the polymer resin and the photopolymerizable monomer were added, 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 through a 0.45 μm filter to remove impurities, thereby preparing each photosensitive resin composition.

[0253] [Table 1]

[0254] (Unit: wt%)

[0255]

[0256] (A) Adhesive resin

[0257] Acrylic adhesive resin (SP-RY38; Resonac Corporation)

[0258] (B) Photopolymerizable monomer

[0259] (B-1) Preparation of photopolymerizable monomer of Example 1

[0260] (B-2) Preparation of photopolymerizable monomer of Example 2

[0261] (B-3) Preparation of photopolymerizable monomer of Example 3

[0262] (B-4) Preparation of photopolymerizable monomer of Example 4

[0263] (B-5) Preparation of photopolymerizable monomer of Example 5

[0264] (B-6) Photopolymerizable monomer of photopolymerizable monomer 6

[0265] (B-7) Photopolymerizable monomer of photopolymerizable monomer 7

[0266] (B-8) Photopolymerizable monomer of comparative preparation example 1

[0267] (B-9) Photopolymerizable monomer of comparative preparation example 2

[0268] (C) Photopolymerization initiator

[0269] Oxime initiator (SPI-03, Sanwa Chemicals)

[0270] (D) Solvent

[0271] Propylene glycol monomethyl ether acetate (PGMEA, DKS Co.)

[0272] Evaluation

[0273] After confirming that the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were all transparent, the refractive index at 550 nm was measured. Thereafter, each composition was coated on an 8-inch silicon wafer at a rotation speed capable of exhibiting a similar thickness using a SEMES K-SPIN, followed by soft baking on a hot plate at 100°C, and pattern exposure on an i-line stepper manufactured by Nikon Corporation under exposure conditions of (dose: 200 mJ / cm, focus: -0.3). During the exposure, the coated substrate was developed to show a pattern after measuring the thickness using a TENCOR. Here, EHD-100S solution (TMAH) was used as a developer, and the time (seconds) required for the pattern to appear (BP) was measured.

[0274] The pattern on the developed substrate was examined by a CD-SEM manufactured by Hitachi, Ltd. to confirm the sensitivity and residue. The pattern was confirmed to be a 96-μm negative pattern, and a large-area residue was confirmed using an Olympus optical microscope, and the results are shown in Table 2. The evaluation criteria for the development and pattern linearity are shown in Table 3.

[0275] [Table 2]

[0276]

[0277] [Table 3]

[0278] Developability Pattern linearity ◎ No residue Very good linearity ○ Only slight residue present around the pattern Excellent linearity △ Residue occurred in all areas Lack of linearity X Not developed Very poor linearity

[0279] From the above evaluation, it can be seen that the photosensitive resin composition according to some example embodiments is a transparent photosensitive resin composition that not only has a very high refractive index at 550 nm, but also has excellent pattern linearity and residue characteristics even under low-temperature curing conditions, making it suitable for use as a microlens around a color filter in a micro-OLED.

[0280] While the present disclosure has been described in connection with the preferred embodiments of the various applications, it is to be understood that other similar embodiments can be used or modifications and alterations can be made by those skilled in the art without departing from the spirit and scope of the inventive disclosure. It is therefore intended that the present embodiments be considered in all respects as illustrative and not restrictive, the scope of the inventive disclosure being indicated by the appended claims rather than the foregoing description.

Claims

1. A photosensitive resin composition, comprising: Adhesive resin; Photopolymerizable monomers; Photopolymerization initiator; as well as Solvent, The photopolymerizable monomer is represented by chemical formula 1: In chemical formula 1, R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. R 3 and R 4 Each is independently a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl. L 1 and L 2 Each is independently a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, or a substituted or unsubstituted C6 to C20 arylene. L 3 To L 6 Each is independently a substituted or unsubstituted C1 to C20 alkylene group, and m and n are each an independent integer from 0 to 4.

2. The photosensitive resin composition according to claim 1, wherein... L 1 and L 2 Each is an unsubstituted C6 to C20 arylene group.

3. The photosensitive resin composition according to claim 1, wherein... L 1 and L 2 Each is independently a C6 to C20 arylene group substituted with a halogenated group and / or a C1 to C20 alkyl group substituted with a halogenated group.

4. The photosensitive resin composition according to claim 1, wherein... L 1 and L 2 Each is independently an unsubstituted C1 to C20 alkylene group.

5. The photosensitive resin composition according to claim 1, wherein... L 1 and L 2 Each is independently an unsubstituted C3 to C20 cycloalkylene group.

6. The photosensitive resin composition according to claim 1, wherein... L 3 To L 6 They are all the same.

7. The photosensitive resin composition according to claim 1, wherein... The photopolymerizable monomer is represented by any one of chemical formulas 1-1 to 1-7:

8. The photosensitive resin composition according to claim 1, wherein... Based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: 10 wt% to 30 wt% of the adhesive resin; 3 wt% to 15 wt% of the photopolymerizable monomer; 0.1 wt% to 5 wt% of the photopolymerization initiator; and The remainder of the solvent.

9. The photosensitive resin composition according to claim 1, wherein... The photosensitive resin composition further includes malonic acid, 3-amino-1,2-propanediol, silane coupling agent, leveling agent, surfactant, polymerization inhibitor, or a combination thereof as additives.

10. The photosensitive resin composition according to claim 1, wherein... The photosensitive resin composition has a refractive index greater than or equal to 1.62 at 550 nm.

11. The photosensitive resin composition according to claim 1, wherein... The photosensitive resin composition has a transmittance of 90% or more at a range of 400 nm to 700 nm.

12. A photosensitive resin layer, manufactured using the photosensitive resin composition as described in claim 1.

13. A display device comprising the photosensitive resin layer as described in claim 12.

14. The display device according to claim 13, wherein The display device is a miniature organic light-emitting diode (OLED) display device, which includes an OLED substrate on a silicon wafer and a color filter layer located on the OLED substrate. The color filter layer converts white light generated from the OLED substrate into light of various colors. The photosensitive resin layer as described in claim 12 is located on the organic light-emitting diode 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.

15. A method for manufacturing a photosensitive resin layer, comprising: Coating with the photosensitive resin composition as described in claim 1; Pre-bake at 100°C or lower after coating; as well as Exposed to the i-line after pre-baking, and development.

Images