Photosensitive resin composition, photosensitive resin layer using same, display device, and method of manufacturing photosensitive resin layer

Abstract

Provided are a photosensitive resin composition, a photosensitive resin layer manufactured using the 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 polymer resin having a refractive index of 1.66 or more; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a solvent, in which the polymer resin has a repeating structural unit including a group derived from an anhydride.

Description

[0001] Cross-citation of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0065471, filed with the Korean Intellectual Property Office on May 20, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a photosensitive resin composition, a photosensitive resin layer using the same, a display device, and a method for manufacturing the photosensitive resin layer. Background Technology

[0004] Recently, there has been increasing interest in self-emissive (emitting) micro-organic light-emitting diode (OLED) display panels for use in virtual reality (VR), augmented reality (AR), and mixed reality (MR) devices.

[0005] In micro-OLED display panels, where pixel sizes are 10 times smaller than those of regular OLED display panels, it is difficult to form red (R) / green (G) / blue (B) emitting layers using traditional fine metal mask (FMM) technology. In other words, if traditional LCD displays are used in VR, AR, and other devices, the color filters may have excessively large pattern sizes, thus failing to improve resolution.

[0006] Therefore, OLED-on-Silicon (OLEDos) technology is currently being introduced to achieve high resolutions of approximately 4000 pixels per inch (ppi) or higher. This technology uses OLEDs deposited on a silicon wafer as a backlight to pattern color filters on top of them. While color filters used in conventional LCDs are patterned on glass at approximately 100 μm and cured by exposure and post-baking at temperatures of approximately 230°C or higher, color filters on OLEDos cannot be processed at high temperatures due to the limitations of OLEDs and must therefore be cured at lower temperatures. Furthermore, micropatterning is crucial for improving resolution. Due to the small size of VR and AR devices, micropatterning is essential for achieving the required resolution.

[0007] However, since curing only occurs at low temperatures (below 100°C), color filters made from existing materials suffer from insufficient developability and patterning capabilities. Therefore, research on low-temperature curable transparent materials with excellent color filter adhesion, developability, and fine patterning capabilities is ongoing. Summary of the Invention

[0008] Some embodiments provide a photosensitive resin composition that can be fully cured even at low temperatures, has transparency, excellent adhesion to color filters, and excellent developability and fine patterning capability.

[0009] Some embodiments provide photosensitive resin layers manufactured using the aforementioned photosensitive resin composition.

[0010] Some embodiments provide a display device that includes the photosensitive resin layer.

[0011] Some embodiments provide methods for manufacturing the photosensitive resin layer.

[0012] Some embodiments provide a photosensitive resin composition comprising (A) a polymeric resin having a refractive index greater than or equal to 1.66; (B) a photopolymerizable monomer; (C) a photopolymerizable initiator; and (D) a solvent, wherein the polymeric resin has repeating structural units comprising moiety derived from acid dianhydrides.

[0013] The structural unit may further include a moiety containing one or more sulfur atoms.

[0014] Groups containing one or more sulfur atoms may include structures represented by any of the chemical formulas 1 to 3.

[0015] [Chemical Formula 1]

[0016]

[0017] [Chemical Formula 2]

[0018]

[0019] [Chemical Formula 3]

[0020]

[0021] In chemical formulas 1 to 3

[0022] X is either *-S-* or *-S(=O)2-*.

[0023] R1 is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0024] L1 to L6 are each independently a substituted or unsubstituted C1 to C20 alkylene or a substituted or unsubstituted C6 to C20 arylene.

[0025] A group containing one or more sulfur atoms may include at least one structure selected from chemical formulas 1-1, 1-2, 2-1 and 3-1.

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 1-2]

[0029]

[0030] [Chemical Formula 2-1]

[0031]

[0032] [Chemical Formula 3-1]

[0033]

[0034] Residues derived from acid anhydrides may include structures represented by chemical formula 4-1 or chemical formula 4-2.

[0035] [Chemical Formula 4-1]

[0036]

[0037] [Chemical Formula 4-2]

[0038]

[0039] In chemical formulas 4-1 and 4-2,

[0040] Y is a single bond or *-C(=O)-*.

[0041] The repeating structural unit in the polymer resin can be represented by any one of the chemical formulas 5 to 8.

[0042] [Chemical Formula 5]

[0043]

[0044] [Chemical Formula 6]

[0045]

[0046] [Chemical Formula 7]

[0047]

[0048] [Chemical Formula 8]

[0049]

[0050] Based on the total amount of the photosensitive resin composition, the content of the polymer resin can be from 10 wt% to 30 wt%.

[0051] The polymer resin can have a weight-average molecular weight of 2,000 g / mol to 20,000 g / mol.

[0052] Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may include: 10 wt% to 30 wt% of (A) a polymer resin; 3 wt% to 15 wt% of (B) a photopolymerizable monomer; 0.1 wt% to 5 wt% of (C) a photopolymerization initiator; and the balance being (D) a solvent.

[0053] The photosensitive resin composition may also include malonic acid, 3-amino-1,2-propanediol, silane coupling agent, leveling agent, surfactant, polymerization inhibitor, or a combination thereof as additives.

[0054] The photosensitive resin composition may have a refractive index greater than or equal to 1.62.

[0055] Another embodiment provides a photosensitive resin layer manufactured using a photosensitive resin composition.

[0056] The photosensitive resin layer can be transparent.

[0057] Another embodiment provides a display device including a photosensitive resin layer.

[0058] The display device can be a micro organic light-emitting diode (micro OLED) display device, which includes an organic light-emitting diode substrate on a silicon wafer and a color filter layer located on the organic light-emitting diode substrate. The color filter layer converts the white light generated by the organic light-emitting diode substrate into light of multiple colors. A photosensitive resin layer 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.

[0059] Some embodiments provide a method for manufacturing a photosensitive resin layer, including coating a photosensitive resin composition; pre-baking the coated layer at a temperature of 100°C or lower; exposing the pre-baked layer to an LED; and developing the layer.

[0060] Other embodiments are included in the following detailed description.

[0061] According to some embodiments, the photosensitive resin composition is a transparent photosensitive resin composition that can be cured at low temperatures of 100°C or lower, exhibiting excellent color filter adhesion, as well as excellent developability and fine patterning capability. Since the above effects can be achieved even at pre-baking temperatures of 100°C or lower via photocuring alone (i-line exposure), the composition is suitable for use as a microlens layer (microlens array) in micro-organic light-emitting diode display devices capable of realizing micropatterns. Attached Figure Description

[0062] Figure 1 This is a schematic diagram illustrating the structure of a miniature organic light-emitting diode display device according to some embodiments. Detailed Implementation

[0063] The embodiments will now be described in detail. However, these embodiments are exemplary, and the invention is not limited thereto; the invention is defined by the scope of the claims.

[0064] In this document, unless otherwise specifically defined, "alkyl" refers to C1 to C20 alkyl, "alkenyl" refers to C2 to C20 alkenyl, "cycloalkenyl" refers to C3 to C20 cycloalkenyl, "heterocyclic alkenyl" refers to C3 to C20 heterocyclic alkenyl, "aryl" refers to C6 to C20 aryl, "aranealkyl" refers to C6 to C20 aranealkyl, "alkylene" refers to C1 to C20 alkylene, "arylene" refers to C6 to C20 arylene, "alkylarylene" refers to C6 to C20 alkylarylene, "heteroarylene" refers to C3 to C20 heteroarylene, and "alkoxide" refers to C1 to C20 alkoxide.

[0065] In this document, unless otherwise specifically defined, "substituted" means that at least one hydrogen atom of a compound is replaced by a substituent selected from the following: halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, imino, azide, amide, hydrazyl, hydrazone, carbonyl, carbamoyl, mercapto, ester, ether, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocyclic alkyl, C2 to C20 heterocyclic alkenyl, C2 to C20 heterocyclic alkynyl, C3 to C20 heterocyclic aryl, or combinations thereof.

[0066] In this document, unless otherwise defined, "heterogeneous" refers to a chemical formula containing at least one heteroatom of N, O, S, and P.

[0067] In this document, unless otherwise specifically defined, "(meth)acrylate" refers to "acrylate" and "methacrylate", and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid".

[0068] In this document, unless otherwise defined, the term "composite" refers to a blend or copolymer. Furthermore, "copolymer" refers to a range from block copolymer to random copolymer, and "polymer" refers to a range from block copolymer to random copolymer.

[0069] In the chemical formulas of this specification, unless otherwise specifically defined, when the position of a chemical bond is not shown where it should be given, hydrogen is bonded at that position.

[0070] In this document, unless otherwise defined, "*" refers to the connecting part between the same or different atoms or chemical formulas.

[0071] The photosensitive resin composition according to some embodiments includes (A) a polymer resin having a refractive index greater than or equal to 1.66; (B) a photopolymerizable monomer; (C) a photopolymerizable initiator; and (D) a solvent, wherein the polymer resin has repeating structural units, said structural units including groups derived from acid anhydrides.

[0072] Traditional color photoresists are negative photosensitive liquid materials used for red, green, and blue patterns. Technological development has consistently focused on gradually modifying the composition of these liquid materials. For example, color purity can be improved by modifying the type or content of the pigment dispersion (i.e., the coloring material) that achieves the color pattern; patterning ability can be improved by modifying the composition of the binder resin or photopolymerization initiator; or coating performance and color uniformity can be improved by using other additives (such as leveling agents).

[0073] This invention is not an invention of color photoresist for manufacturing the aforementioned conventional color filters, but rather an invention of microlenses for use in miniature organic light-emitting diode (OLED) display devices. The microlenses exhibit excellent adhesion to low-temperature curing color filters, and therefore can be applied to display devices that include low-temperature curing color filters.

[0074] Microdisplays are a technology that transmits image information to a display with a screen size of 1 inch or smaller using an optical system. Here, because high resolution must be achieved within a very small area, complementary metal-oxide-semiconductor (CMOS) semiconductors are used on a silicon wafer substrate. CMOS Back panel.

[0075] Among them, miniature organic light-emitting diode displays use organic light-emitting diodes as backlights to emit light and require color filters that are cured at low temperatures. On the other hand, as pixel sizes shrink, highly sensitive materials are needed to reproduce accurate light colors.

[0076] Because traditional semiconductor CMOS processes use hexa-methyl-di-silazane (HDMS) deposition to adhere color filters, low-temperature curing is not feasible. To address this issue, extensive research has been conducted on alternative materials. Through extensive research, the inventors have developed a photosensitive resin composition for microlenses that exhibits excellent developability and fine patterning capabilities while maintaining low-temperature curing, thus completing this invention.

[0077] Specifically, the photosensitive resin composition according to some embodiments is a low-temperature curable transparent material with high adhesion to color filters, low residue (excellent developability), and excellent pattern linearity (excellent fine patterning capability). In particular, the photosensitive resin composition according to some embodiments is a transparent material suitable for next-generation displays requiring transparency (crack resistance) and precise patterning to fit desired areas, such as display devices for virtual reality (VR), augmented reality (AR), and mixed reality (MR), such as micro-organic light-emitting diode display devices. In other words, the photosensitive resin composition according to some embodiments can be a colorant-free composition, for example, a transparent photosensitive resin composition, and therefore can also exhibit excellent light transmittance.

[0078] More specifically, the photosensitive resin composition according to some embodiments can improve residue properties (developability) and pattern linearity (fine patterning capability) by controlling the refractive index of the polymer resin, particularly the refractive index of the polymer resin at 550 nm, such that the refractive index is greater than or equal to 1.66.

[0079] The following is a detailed description of each component.

[0080] (A) Polymer resin

[0081] As described above, the photosensitive resin composition according to some embodiments includes a polymer resin, wherein the refractive index of the polymer resin at 550 nm can be controlled to significantly improve residue properties, pattern linearity, and adhesion to color filters. Specifically, the refractive index of the polymer resin at 550 nm can be in the range of 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, or for example 1.68 to 1.8.

[0082] In order to control the refractive index at 550 nm as shown above, the polymer resin in the photosensitive resin composition according to some embodiments includes repeating structural units, wherein the structural units may include two residual groups, such as "a group derived from an acid anhydride" and "a group containing one or more sulfur atoms".

[0083] For example, a group containing one or more sulfur atoms may include at least two sulfur atoms, such as at least three sulfur atoms, or at least four sulfur atoms. The more sulfur atoms, the higher the refractive index of the polymer resin at 550 nm, thereby maximizing the improvement in developability and pattern linearity.

[0084] On the other hand, the polymer resin must include "groups derived from acid anhydrides".

[0085] If the polymer resin only includes "groups containing one or more sulfur atoms", the refractive index at 550 nm may be difficult to control at 1.66 or higher, leading to deterioration in developability and pattern linearity. Furthermore, the resin must be a polymer resin; however, if a monomolecular resin is used, even if the refractive index at 550 nm is controlled within the range, compatibility with other components (e.g., photopolymerizable monomers or photopolymerization initiators) may deteriorate, resulting in very poor developability and pattern linearity.

[0086] For example, a group containing one or more sulfur atoms may include, but is not necessarily limited to, any of the structures represented by chemical formulas 1 to 3.

[0087] [Chemical Formula 1]

[0088]

[0089] [Chemical Formula 2]

[0090]

[0091] [Chemical Formula 3]

[0092]

[0093] In chemical formulas 1 to 3

[0094] X can be *-S-* or *-S(=O)2-*.

[0095] R 1 It can be a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl, and

[0096] L 1 To L 6 Each can be independently a substituted or unsubstituted C1 to C20 alkylene or a substituted or unsubstituted C6 to C20 arylene.

[0097] For example, a group containing one or more sulfur atoms may include, but is not limited to, at least one structure selected from chemical formulas 1-1, 1-2, 2-1 and 3-1.

[0098] [Chemical Formula 1-1]

[0099]

[0100] [Chemical Formula 1-2]

[0101]

[0102] [Chemical Formula 2-1]

[0103]

[0104] [Chemical Formula 3-1]

[0105]

[0106] For example, groups derived from acid anhydrides may include structures represented by chemical formula 4-1 or chemical formula 4-2.

[0107] [Chemical Formula 4-1]

[0108]

[0109] [Chemical Formula 4-2]

[0110]

[0111] In chemical formulas 4-1 and 4-2,

[0112] Y is a single bond or *-C(=O)-*.

[0113] For example, repeating structural units in polymer resins can be represented by chemical formulas 5 to 8, but are not necessarily limited to these.

[0114] [Chemical Formula 5]

[0115]

[0116] [Chemical Formula 6]

[0117]

[0118] [Chemical Formula 7]

[0119]

[0120] [Chemical Formula 8]

[0121]

[0122] For example, based on the total amount of the photosensitive resin composition, the content of the polymer resin can be from 10 wt% to 30 wt%, for example, from 15 wt% to 25 wt%. For example, based on the total solids content of the photosensitive resin composition, the content of the polymer resin can be from 40 wt% to 80 wt%, for example, from 50 wt% to 70 wt%. When the weight of the polymer resin is controlled within the above range, the difference between the refractive index of the photosensitive resin composition at 550 nm and the refractive index of the polymer resin at 550 nm according to some embodiments can be minimized, ultimately maximizing the improvement of the developability and pattern linearity of the photosensitive resin composition.

[0123] For example, the polymer resin can have a weight average molecular weight of 20,000 g / mol to 80,000 g / mol. When the weight average molecular weight of the polymer resin is controlled within the above range, compatibility with other components (such as photopolymerizable monomers and photopolymerizable initiators described later) can be improved.

[0124] In addition to polymer resins, the photosensitive resin compositions according to some embodiments may further include conventionally used adhesive resins, such as acrylic adhesive resins, epoxy adhesive resins, or combinations thereof, in addition to polymer resins.

[0125] Acrylic adhesive resin is a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer copolymerized therewith, and is a resin comprising one or more repeating units of acrylic acid.

[0126] The first olefinic unsaturated monomer can be an olefinic unsaturated monomer that includes at least one carboxyl group, and specific examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0127] The content of the first olefinic unsaturated monomer can be 5 wt% to 50 wt%, for example 10 wt% to 40 wt%, based on the total amount of acrylic adhesive resin.

[0128] Examples of second-ene unsaturated monomers include: aromatic vinyl compounds, such as styrene, α-methylstyrene, vinyltoluene, vinyl benzyl methyl ether, and the like; 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, phenyl (meth)acrylate, and the like; unsaturated aminoalkyl carboxylic acid ester compounds, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, and the like; vinyl carboxylic acid ester compounds, such as vinyl acetate, vinyl benzoate, and the like; unsaturated glycidyl carboxylic acid ester compounds, such as glycidyl (meth)acrylate and the like; vinyl cyanide compounds, such as (meth)acrylonitrile and the like; unsaturated amide compounds, such as (meth)acrylamide and the like; etc., and said compounds may be used alone or in mixtures of two or more thereof.

[0129] Specific examples of acrylic adhesive resins may be (meth)acrylic acid / benzyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene copolymers, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymers, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymers, etc., but are not limited to these, and may be used alone or as a mixture of two or more.

[0130] Acrylic adhesive resins can have acid values ​​ranging from 30 mg / g to 180 mg / g and weight-average molecular weights ranging from 3,000 g / mol to 20,000 g / mol. When the acid value and weight-average molecular weight of the acrylic adhesive resin are within the above ranges, it exhibits excellent patterning properties, and the resulting film can possess excellent mechanical and thermal properties.

[0131] When an epoxy adhesive resin is additionally included in the photosensitive resin composition according to some embodiments, heat resistance can be improved. The epoxy adhesive resin may include, but is not limited to, phenolic epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or combinations thereof.

[0132] (B) Photopolymerizable monomers

[0133] According to some embodiments, the photopolymerizable monomer in the photosensitive resin composition may be a single compound or a mixture of two different types of compounds.

[0134] For example, the photopolymerizable monomer can be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one olefinic unsaturated double bond.

[0135] Photopolymerizable monomers have olefinic unsaturated double bonds, which can induce full polymerization during exposure in the patterning process, resulting in patterns with excellent heat resistance, light resistance and chemical resistance.

[0136] Specific examples of photopolymerizable monomers 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, and pentaerythritol hexa(meth)acrylate. Acrylic esters, 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, tri(meth)acryloyloxyethyl phosphate, phenolic epoxy (meth)acrylate, ethoxylated biphenylfluorene diacrylate, ethoxylated naphthalene diacrylate, ethoxylated sulfur diacrylate, etc.

[0137] Commercially available examples of photopolymerizable monomers are as follows. Examples of (meth)acrylate monofunctional esters may include Aronix. (Toa Synthetic Chemical Industry Co., Ltd.); Kayarad (Nippon Kayaku Co., Ltd.); (Osaka Organic Chemical Industry Co., Ltd.) etc. Examples of difunctional (meth)acrylates may include (Toa Synthetic Chemical Industry Co., Ltd.), Cayalard (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemicals 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 (Hanong Chemical Co., Ltd., etc.). Examples of trifunctional esters of (meth)acrylate may include Anix. (Toa Synthetic Chemical Industry Co., Ltd.), Cayalard (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemical Industry Co., Ltd.), etc. These can be used alone or as a mixture of two or more.

[0138] Photopolymerizable monomers can be treated with acid anhydrides to improve their developability.

[0139] For example, based on the total amount of the photosensitive resin composition, the content of photopolymerizable monomers can be from 3 wt% to 15 wt%, for example, from 5 wt% to 10 wt%. For example, based on the total solids content of the photosensitive resin composition, the content of photopolymerizable monomers can be from 20 wt% to 60 wt%, for example, from 30 wt% to 50 wt%. When the photopolymerizable monomers are included in the ranges described above, the photopolymerizable monomers are fully cured during exposure in the patterning process and have excellent reliability, and the developability with alkaline developers can be improved.

[0140] (C) Photopolymerization initiator

[0141] The photosensitive resin composition according to some embodiments includes a photopolymerization initiator. The photopolymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, etc.

[0142] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-but-1-one, and the like.

[0143] Examples of benzophenone compounds include benzoyl benzoate, benzoyl benzoate, 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.

[0144] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0145] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like.

[0146] Examples of 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, and 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-piperyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine and the like.

[0147] Examples of oxime compounds can be O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylthiophenyl)-but-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-but-1-one, oxime-O-acetate, etc.

[0148] In addition to the compounds mentioned above, photopolymerization initiators can also be used with, for example, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, etc.

[0149] For example, based on the total amount of the photosensitive resin composition, the content of the photopolymerization initiator can be from 0.1 wt% to 5 wt%, for example, from 0.5 wt% to 3 wt%. For example, based on the total solids content of the photosensitive resin composition, the content of the photopolymerization initiator can be from 1 wt% to 5 wt%, for example, from 1.5 wt% to 3 wt%. When the photopolymerization initiator is included within the above ranges, the photopolymerization reaction occurs sufficiently during exposure in the patterning process for manufacturing microlenses, thereby producing excellent sensitivity and improved light transmittance.

[0150] (D) Solvent

[0151] The solvent can be a material that is compatible with polymer resins, photopolymerization monomers, and photopolymerization initiators but does not react with them.

[0152] Examples of solvents may include: alcohols, such as methanol, ethanol, and the like; ethers, such as dichloroethyl ether, 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; celux acetate, such as methyl celux acetate, ethyl celux acetate, diethyl celux acetate, and the like; carbitol, 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 ethers. Esters, 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-pentanone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactic acid esters, such as methyl lactate, ethyl lactate and the like; alkyl oxyacetic acid esters, such as methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetic acid and the like; alkyl alkoxyacetic acid esters, such as methoxy... Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxypropionic acid esters, such as methyl 3-oxypropionic acid, ethyl 3-oxypropionic acid and the like; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid and the like; alkyl 2-oxypropionic acid esters, such as methyl 2-oxypropionic acid, ethyl 2-oxypropionic acid, propyl 2-oxypropionic acid and the like; alkyl 2-alkoxypropionic acid esters, such as methyl 2-methoxypropionic acid, ethyl 2-methoxypropionic acid... Esters, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate and the like; 2-oxy-2-methylpropionates, such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate and the like; monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters, such as 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, 2-hydroxy-3-methylethylbutyrate and the like; keto esters, such as ethyl pyruvate and the like. Alternatively, high-boiling-point solvents may be used, such as N-methylformamide, N,N-dimethylformamide, N-methylformaniline, 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, phenylcelusyl acetate and the like.

[0153] Considering compatibility and reactivity, it is preferable to use: glycol 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 celusone acetate and the like; esters, such as 2-hydroxyethyl propionate and the like; carbitol, such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like.

[0154] Based on the total amount of the photosensitive resin composition, the solvent content can be in the balance, for example, 50 wt% to 90 wt%, 60 wt% to 80 wt%, or 70 wt% to 80 wt%. If the solvent is included in this range, the photosensitive resin composition can have a suitable viscosity, thereby improving processability in the production of photosensitive resin layers, especially microlenses.

[0155] (E) Other additives

[0156] Additionally, the photosensitive resin composition may also include additives such as malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, surfactants, polymerization inhibitors, or combinations thereof.

[0157] Silane-based coupling agents can have reactive substituents (such as vinyl, carboxyl, methacryloyloxy, isocyanate, or epoxy groups) to improve adhesion to the substrate. However, if a silane-based coupling agent is used, since the photosensitive resin composition according to some embodiments is a colorant-free composition, i.e., a transparent photosensitive resin composition, the effect of improving the adhesion to the color filter may not be achieved if the refractive index of the polymer resin at 550 nm is not controlled as described above.

[0158] Examples of silane-based coupling agents may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidyl ether propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. These can be used alone or in combination of two or more.

[0159] Based on 100 parts by weight of the photosensitive resin composition, the content of the silane coupling agent can be from 0.01 parts by weight to 10 parts by weight. If the silane coupling agent is included in the above range, adhesion, storage capacity, etc., are improved.

[0160] In addition, depending on the requirements, the photosensitive resin composition may also include surfactants, such as fluorinated surfactants and / or silicone surfactants, to improve coating performance and prevent defect formation.

[0161] 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. etc.; Asahi Glass Co., Ltd. etc.; Toray Silicone Oil Co., Ltd. wait.

[0162] 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.

[0163] Based on 100 parts by weight of the photosensitive resin composition, the content of surfactant can be from 0.001 parts by weight to 5 parts by weight. If the surfactant is included in this range, uniform coating can be ensured, stains may not be generated, and wettability on indium zinc oxide (IZO) substrates or glass substrates is improved.

[0164] 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.

[0165] 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.

[0166] Catechol compounds can be used in the form of dispersions. Based on the total amount of the photosensitive resin composition, the content of polymerization inhibitors in dispersion form can be from 0.001 wt% to 3 wt%, for example, from 0.01 wt% to 1 wt%. If the polymerization inhibitors are within the above range, the problem of room temperature aging can be solved and the decrease in sensitivity and surface peeling can be prevented.

[0167] In addition, unless the additives would reduce the performance of the photosensitive resin composition, the photosensitive resin composition may include a predetermined amount of other additives (such as stabilizers).

[0168] The photosensitive resin composition according to some embodiments may be positive or negative, but should be negative to completely remove residues from the patterned exposed areas after exposure and development of the composition with light-shielding properties.

[0169] Meanwhile, the photosensitive resin composition according to some embodiments can have a refractive index greater than or equal to 1.62 (at 550 nm), for example, a refractive index greater than or equal to 1.62 and less than 1.66 (at 550 nm). When the refractive index of the photosensitive resin composition comprising the polymer resin at 550 nm is controlled as described above, it can be beneficial to improve developability and fine patterning capability.

[0170] Some embodiments provide photosensitive resin layers manufactured by low-temperature curing, exposure, and development of the above-described photosensitive resin composition. The difference compared to conventional liquid crystal display or semiconductor processes is that a post-curing (post-baking) step is not required.

[0171] The method for manufacturing the photosensitive resin layer is as follows.

[0172] (1) Coating and film formation (low-temperature curing)

[0173] A photosensitive resin composition is coated onto a pre-treated substrate, such as a silicon wafer, using methods such as spin coating, slit coating, roller coating, screen printing, or a coater to achieve the desired thickness. The substrate is then heated at 100°C for 1 to 10 minutes to remove the solvent, thereby forming a photosensitive resin layer. This step may improve image quality, among other things.

[0174] (2) Exposure

[0175] After placing a mask with the desired pattern on the obtained photosensitive resin layer, the surface is exposed by irradiating it with photochemically active I-rays. As the light source for irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc., can be used, and in some cases, X-rays, electron beams, etc., can be used.

[0176] For example, when using a high-pressure mercury lamp, the exposure process uses 500 mJ / cm². 2 Or even a lower light dose (using a 365nm sensor). However, the light dose can vary depending on the type of each component, the combination ratio, and the dry film thickness. This step allows for fine-tuning of the pixel size, thereby achieving high resolution.

[0177] (3) Development

[0178] In the development method, after the exposure step, an alkaline aqueous solution is used as the developer to dissolve and remove unwanted portions, leaving only the exposed areas to form a pattern. This step helps to create a contour for high resolution and ensures color uniformity for improved sharpness.

[0179] Some embodiments provide a display device that includes a photosensitive resin layer.

[0180] The display device can be a miniature organic light-emitting diode (OLED) display device.

[0181] A miniature organic light-emitting diode (OLED) display device may include an OLED substrate deposited on a silicon wafer and a color filter layer located on the OLED substrate. The color filter layer converts white light generated by the OLED substrate into light of various colors, including a red filter, a green filter, and a blue filter. Furthermore, a photosensitive resin layer (i.e., a microlens layer) is located on the OLED substrate and the color filter layer. In other words, the microlens layer may surround the color filter layer on the OLED substrate.

[0182] For example, a miniature organic light-emitting diode (OLED) display device includes: an organic light-emitting diode substrate on a silicon wafer; an inorganic layer stacked on the organic light-emitting diode substrate; and a color filter layer stacked on the inorganic layer, wherein the color filter layer converts white light generated by the organic light-emitting diode substrate into light of multiple colors, and the color filter layer may include a red color filter, a green color filter, and a blue color filter. Furthermore, a photosensitive resin layer (i.e., a microlens layer) is located on the inorganic layer and the color filter layer. That is, the microlens layer may surround the color filter layer on the inorganic layer.

[0183] For example, a miniature organic light-emitting diode (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, the color filter layer converting white light generated by the OLED substrate into light of multiple colors, wherein the color filter layer includes a red color filter, a green color filter, and a blue color filter. Furthermore, a photosensitive resin layer (i.e., a microlens layer) is located on the adhesive protective layer and the color filter layer. That is, the microlens layer may surround the color filter layer on the adhesive protective layer.

[0184] Traditionally, OLED substrates have been used, where OLEDs are deposited on glass or polyimide substrates. However, according to some embodiments, miniature OLED display devices may have an advantage in realizing microdisplays because the OLEDs are deposited on silicon wafers. These microdisplays are attracting significant attention as next-generation displays and are expected to be used in devices such as MR (Mixed Reality). In fact, Apple, Meta, and LG Display have all entered or announced their entry into the next-generation MR device market.

[0185] The micro organic light-emitting diode display device with the above structure can be driven on a pixel-by-pixel basis by depositing white organic light-emitting diodes (White OLED, WOLED) on a highly integrated silicon wafer, and the transmission wavelength can be easily controlled by a patterned color filter layer with a resolution of less than or equal to 3μm, thereby achieving high color reproduction and ensuring high resolution.

[0186] For example, the thickness of the adhesive protective layer can be less than or equal to 1 μm. In this case, the aforementioned effects (i.e., improved adhesion to the color filter and improved residue properties) can be further maximized.

[0187] For example, the thickness of the color filter layer can be from 1.1 μm to 1.6 μm.

[0188] Controlling the thickness of the color filter layer in the manner described above may be more conducive to realizing miniature organic light-emitting diode display devices.

[0189] For example, the thickness of the inorganic layer can be less than or equal to 2 μm. Even when using white organic light-emitting diodes (OLEDs), light does not always diffuse perpendicular to the OLED substrate, inevitably resulting in color mixing of red, green, and blue. Therefore, in the past, inorganic layers were deposited on the OLED substrate to prevent this color mixing. However, since color mixing cannot be completely prevented even with the deposition of an inorganic layer, in some embodiments, slight light leakage can be prevented by thinning the inorganic layer, for example, controlling its thickness to less than or equal to 2 μm.

[0190] Ultimately, the photosensitive resin composition according to some embodiments allows the production of a cured layer solely through low-temperature (100°C) curing during pre-baking and i-line photocuring, which, as mentioned above, inevitably results in a significant difference in achievable resolution compared to conventional display devices.

[0191] Preferred embodiments of the present invention will be described below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to these embodiments.

[0192] (Example)

[0193] (Preparation of polymer resins)

[0194] Preparation Example 1: Synthesis of the material represented by chemical formula 5

[0195] (Reaction Scheme 1)

[0196]

[0197] Compound 1a (10.0 mmol), compound 1b (4.00 mmol), and potassium carbonate (K₂CO₃, 4.00 mmol) were added to 30.0 mL of N,N-dimethylformamide (DMF), 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. The precipitate was separated by vacuum filtration, washed with distilled water, and recrystallized from toluene to obtain compound 1c.

[0198] (Reaction Scheme 2)

[0199]

[0200] Compound 1c (5.00 mmol), compound 1d (50.0 mmol), and potassium carbonate (K₂CO₃, 25.0 mmol) were added to 20.0 mL of 1,4-dioxane / H₂O (v / v) and stirred overnight at room temperature. After confirming the depletion of compound 1c by thin-layer chromatography, the reaction mixture was added to distilled water to form a precipitate. The precipitate was separated by pressure filtration, washed with distilled water, and dried overnight in a vacuum oven. Recrystallization from toluene yielded compound 1e.

[0201] (Reaction Scheme 3)

[0202]

[0203] Compound 1e (10.0 mmol) was added to 30.0 mL of toluene along 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, compound 1f was purified by column chromatography (eluent: n-hexane / ethyl acetate) to obtain compound 1f.

[0204] (Reaction Scheme 4)

[0205]

[0206] Compound 1f (10.0 mmol), compound 1 g (11.0 mmol), butylated hydroxytoluene (BHT, 0.5 wt%), and diazabicycloundecene (DBU, 0.50 mmol) were added to 30.0 mL of cyclohexanone. The reaction mixture was heated to 110 °C and then stirred for 6 hours to prepare a polymer resin comprising repeating structural units represented by Formula 5 (weight average molecular weight: 4,900 g / mol). The refractive index at 550 nm was 1.69.

[0207] Preparation Example 2: Synthesis of a material represented by chemical formula 6

[0208] (Reaction Scheme 5)

[0209]

[0210] Compound 1a (10.0 mmol) was added to 1.50 mL of acetic acid, and excess 30% hydrogen peroxide was added at room temperature. The reaction mixture was stirred overnight at 120 °C, and then extracted with dichloromethane (DCM). The resulting organic layer was passed through MgSO4, and the solvent was removed under reduced pressure. Compound 2a was purified by column chromatography (eluent: DCM / n-hexane) to obtain the compound.

[0211] (Reaction Scheme 6)

[0212]

[0213] The synthesis method of compound 2b is the same as that of compound 1c, except that compound 2a is used instead of compound 1a.

[0214] (Reaction Scheme 7)

[0215]

[0216] The synthesis method of compound 2c is the same as that of compound 1e, except that compound 2b is used instead of compound 1c.

[0217] (Reaction Scheme 8)

[0218]

[0219] The synthesis method of compound 2d is the same as that of compound 1f, except that compound 2c is used instead of compound 1e.

[0220] (Reaction Scheme 9)

[0221]

[0222]

[0223] A polymer resin comprising repeating structural units represented by chemical formula 6 (weight-average molecular weight: 4,600 g / mol) was synthesized in the same manner as that used to synthesize compound 1f, except that compound 2d was used instead of compound 1f. The refractive index at 550 nm was 1.68.

[0224] Preparation Example 3: Synthesis of a material represented by chemical formula 7

[0225] (Reaction Scheme 10)

[0226]

[0227] Compound 3a (10.0 mmol) and compound 1b (20.0 mmol) were dissolved in 40.0 mL of tetrahydrofuran (THF) at 0 °C, and then stirred at room temperature for 2 hours. After removing the solvent under reduced pressure, the reaction mixture was dissolved in dichloromethane (DCM), and the resulting solution was washed with 1 N hydrochloric acid aqueous solution. The organic layer was then passed through magnesium sulfate. The obtained organic layer was concentrated under reduced pressure to obtain compound 3b, which was used in subsequent reactions without additional purification.

[0228] (Reaction Scheme 11)

[0229]

[0230] The synthesis method of compound 3c is the same as that of compound 1e, except that compound 3b is used instead of compound 1c.

[0231] (Reaction Scheme 12)

[0232]

[0233] The synthesis method of compound 3d is the same as that of compound 1f, except that compound 3c is used instead of compound 1e.

[0234] (Reaction Scheme 13)

[0235]

[0236]

[0237] A polymer resin comprising repeating structural units represented by Formula 7 (weight-average molecular weight: 4,300 g / mol) was synthesized in the same manner as the material synthesized by Formula 5, except that compound 3d was used instead of compound 1f. The refractive index at 550 nm is 1.66.

[0238] Preparation Example 4: Synthesis of materials represented by chemical formula 8

[0239] (Reaction Scheme 14)

[0240]

[0241] The synthesis method of compound 4b is the same as that of compound 1e, except that compound 4a is used instead of compound 1c.

[0242] (Reaction Scheme 15)

[0243]

[0244] The synthesis method of compound 4c is the same as that of compound 1f, except that compound 4b is used instead of compound 1e.

[0245] (Reaction Scheme 16)

[0246]

[0247] A polymer resin comprising repeating structural units represented by Formula 8 (weight-average molecular weight: 5,100 g / mol) was synthesized in the same manner as the material synthesized by Formula 5, except that compound 4c was used instead of compound 1f. The refractive index at 550 nm is 1.67.

[0248] Comparative Preparation Example 1: Synthesis of Materials Represented by Chemical Formula C-1

[0249] (Reaction Scheme 17)

[0250]

[0251] A solution of compound 5a (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. Then, compound 1a (10.0 mmol) was added, the temperature was raised to 120 °C, and the mixture was stirred for 12 hours. After confirming the depletion of compound 1a by thin-layer chromatography, the reaction mixture was added to distilled water to produce a precipitate. This precipitate was separated by vacuum filtration, washed with distilled water, and recrystallized from toluene to obtain compound 5b.

[0252] (Reaction Scheme 18)

[0253]

[0254] N,N-dimethylaniline (15.0 mmol) was added to compound 5b (5.00 mmol) dissolved in 30.0 mL of tetrahydrofuran (THF). After cooling the solution to 0 °C, a solution of compound 5c (20.0 mmol) dissolved in 10.0 mL of THF was slowly added. The reaction mixture was stirred overnight at room temperature, and then a saturated aqueous sodium bicarbonate solution was added. The solution was diluted with distilled water and extracted with chloroform. The organic layer was passed through MgSO4 and concentrated under reduced pressure. The resulting product was purified by column chromatography (eluent: DCM / n-hexane) to obtain compound 5d.

[0255] (Reaction Scheme 19)

[0256]

[0257] A polymer resin comprising repeating structural units represented by chemical formula C-1 was synthesized by stirring the compound (3.00 mmol) at 60 °C for 5 days and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (1.5 wt%) for 20 minutes, followed by irradiation with ultraviolet light using a mercury lamp (Miksa mercury lamp model M-1S) for 30 minutes. The refractive index at 550 nm was 1.65.

[0258] Comparative Preparation Example 2: Synthesis of Materials Represented by Chemical Formula C-2

[0259] (Reaction Scheme 20)

[0260]

[0261] A monomolecular compound represented by the chemical formula C-2 was prepared in the same manner as compound 5d, except that compound 5b was synthesized using compound 1c instead. The refractive index at 550 nm was 1.66.

[0262] (Preparation of photosensitive resin composition)

[0263] Examples 1 to 4 and Comparative Examples 1 and 2

[0264] According to the compositions shown in Table 1, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. During this process, the polymer resin and photopolymerization monomer were added, and the mixture was stirred at room temperature (25°C) for 1 hour, followed by stirring of the entire solution 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.

[0265] [Table 1]

[0266] (Unit: % by weight)

[0267]

[0268] (A) Polymer resin (monomer compound)

[0269] (A-1) Preparation of the polymer resin of Example 1

[0270] (A-2) Preparation of the polymer resin in Example 2

[0271] (A-3) Preparation of the polymer resin in Example 3

[0272] (A-4) Preparation of the polymer resin in Example 4

[0273] (A-5) Comparative preparation example 1 polymer resin

[0274] (A-6) Comparative preparation example 2 polymer resin

[0275] (B) Photopolymerizable monomers

[0276] Ethoxylated bisphenyl fluorene diacrylate (BPF-022L, Hanong Chemical Co., Ltd.)

[0277] (C) Photopolymerization initiator

[0278] Oxime initiator (SPI-03, Samyang Corporation)

[0279] (D) Solvent

[0280] Propylene glycol monomethyl ether acetate (PGMEA, Daicel Inc.)

[0281] evaluate

[0282] After confirming that the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were all transparent, their refractive index at 550 nm was measured. Subsequently, each composition was coated onto an 8-inch silicon wafer using a SEMES K-SPIN at a rotation speed capable of exhibiting similar thicknesses, followed by soft baking on a hot plate at 100°C, and pattern exposure was performed on an i-line stepper manufactured by Nikon Corporation under exposure conditions (dose: 200 ms / focal length: -0.3). During exposure, the thickness was measured using TENCOR, and the coated substrate was developed to reveal the pattern. Here, EHD-100S solution (tetramethyl ammonium hydroxide (TMAH)) was used as the developer, and the time (seconds) required for the pattern to appear was measured (BP).

[0283] The pattern on the developed substrate was examined using a Hitachi CD-SEM to confirm sensitivity and residue. The pattern was confirmed to be a 96 μm negative pattern, and large-area residue was confirmed using an Olympus optical microscope. The results are shown in Table 2. The evaluation criteria for developability and pattern linearity are shown in Table 3.

[0284] [Table 2]

[0285]

[0286] [Table 3]

[0287] radioactivity Pattern linearity ◎ No residue Very good linearity ○ Only slight residue remained around the pattern. Excellent linearity △ Residual matter occurred in all areas. Lack of linearity X No development Very poor linearity

[0288] Evaluations have shown that the photosensitive resin compositions according to some embodiments are transparent and exhibit excellent pattern linearity and residue characteristics even under low-temperature curing conditions, making them suitable for use as microlenses around color filters in micro-organic light-emitting diodes.

[0289] While this disclosure has been described in conjunction with embodiments now considered practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements contained within the spirit and scope of the appended claims. Therefore, it should be understood that the above embodiments are exemplary and not intended to limit the invention in any way.

Claims

1. A photosensitive resin composition, comprising: Polymer resin with a refractive index greater than or equal to 1.66; Photopolymerizable monomers; Photopolymerization initiator; as well as Solvent, The polymer resin described herein has repeating structural units, and The repeating structural unit includes a group derived from an acid dianhydride.

2. The photosensitive resin composition according to claim 1, wherein... The repeating structural unit also includes a group containing one or more sulfur atoms.

3. The photosensitive resin composition according to claim 2, wherein... The group containing one or more sulfur atoms includes structures represented by any of Chemical Formulas 1 to 3: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] in, In chemical formulas 1 to 3 X is *-S-* or *-S(=O)2-*, R1 is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl, and L1 to L6 are each independently a substituted or unsubstituted C1 to C20 alkylene or a substituted or unsubstituted C6 to C20 aryl.

4. The photosensitive resin composition according to claim 2, wherein... The group comprising one or more sulfur atoms includes at least one structure selected from Formula 1-1, Formula 1-2, Formula 2-1, and Formula 3-1: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 2-1] [Chemical Formula 3-1] 5. The photosensitive resin composition according to claim 1, wherein... The groups derived from acid dianhydrides include structures represented by chemical formula 4-1 or chemical formula 4-2: [Chemical Formula 4-1] [Chemical Formula 4-2] in, In chemical formulas 4-1 and 4-2, Y represents a single bond or *-C(=O)-*.

6. The photosensitive resin composition according to claim 1, wherein... The repeating structural unit in the polymer resin is represented by any one of chemical formulas 5 to 8: [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] 7. The photosensitive resin composition according to claim 1, wherein... Based on the total amount of the photosensitive resin composition, the content of the polymer resin is from 10% to 30% by weight.

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

10. 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.

11. The photosensitive resin composition according to claim 1, wherein... The photosensitive resin composition has a refractive index greater than or equal to 1.

62.

12. A photosensitive resin layer, manufactured using the photosensitive resin composition as described in any one of claims 1 to 11.

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 multiple colors. The photosensitive resin layer as described in claim 12 is disposed on the organic light-emitting diode substrate and the color filter layer, and The color filter layer includes a red filter, a green filter, and a blue filter.

15. A method for manufacturing a photosensitive resin layer, comprising: Coating with the photosensitive resin composition as described in claim 1; Pre-baking is performed at 100°C or lower after coating; After the pre-baking process, the image is exposed to the i-line, and Develop the product.

Images