Black light-shielding photosensitive resin composition, black matrix, black light-shielding film, frame, and filling material for splicing area

Abstract

The present application provides a kind of black light-shielding photosensitive resin composition, black matrix, black light-shielding film, frame and filling material of splicing area.The black light-shielding photosensitive resin composition includes resin (A), pigment (B), monomer (C), initiator (D) and solvent (E).Resin (A) includes epoxy resin (A-1) and the resin (A-2) with ethylenic unsaturated functional group.Pigment (B) includes black particle (B-1) and hollow particle (B-2).

Description

Technical Field

[0001] This invention relates to a resin composition, and more particularly to a black opaque photosensitive resin composition, a black matrix, a black opaque film, a border, and a filler material for splicing areas. Background Technology

[0002] MicroLED display modules, due to their large-scale production using splicing technology, require the application of light-shielding materials to reduce defects and light reflection, thereby enhancing the visual experience. This necessitates the creation of optical materials that meet the requirements of the panel module. To meet the optical density (OD) requirements, a certain amount of black pigment paste needs to be added. However, black is a highly reflective material, and increasing its amount can actually increase reflectivity. Furthermore, differences in reactivity between the upper and lower layers of black photoresist can easily cause wrinkled structures, resulting in decreased OD in thinner areas, inconsistent light-shielding properties, and concerns about light leakage. Moreover, highly reactive black photoresist typically has a glossy finish and cannot produce extinction properties, resulting in very low scattering ratios. Summary of the Invention

[0003] The present invention provides a black light-blocking photosensitive resin composition, a black matrix, a black light-blocking film, a border, and a splicing area. The black matrix, black light-blocking film, border, and splicing area formed by the black light-blocking photosensitive resin composition resist structural reflection with low reflectivity and have sufficient light-blocking rate to reduce bright edge phenomenon and improve visual experience.

[0004] The black opaque photosensitive resin composition of the present invention comprises a resin (A), a pigment (B), a monomer (C), an initiator (D), and a solvent (E). The resin (A) comprises an epoxy resin (A-1) and a resin (A-2) having vinyl unsaturated functional groups. The pigment (B) comprises black particles (B-1) and hollow particles (B-2). The epoxy resin (A-1) comprises compounds represented by formula (1), (2), (3), (4), or (5) below.

[0005] Equation (1),

[0006] Equation (2),

[0007] Equation (3),

[0008] Equation (4),

[0009] Equation (5),

[0010] In formulas (1), (2), (3), (4) and (5), R, R', and R'' are each independently at least one substituted cycloalkyl, phenyl, naphthyl, biphenyl, or adamantane.

[0011] In one embodiment of the present invention, the epoxy resin (A-1) comprises a compound represented by formula (6) or formula (7).

[0012] Equation (6),

[0013] In equation (6), R 1 This indicates a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group, where n is an integer from 1 to 10.

[0014] Equation (7),

[0015] In equation (7), m is an integer from 1 to 10.

[0016] In one embodiment of the invention, the black particles (B-1) include carbon black, titanium black, organic black pigments, or combinations thereof.

[0017] In one embodiment of the invention, the hollow particles (B-2) are made of silicon dioxide.

[0018] In one embodiment of the present invention, the particle size variation coefficient (CV) of the hollow particles (B-2) is greater than 1, and the particle size ranges from 1 nm to 1000 nm.

[0019] In one embodiment of the present invention, when the total amount of resin (A) is 100% by mass, the content of epoxy resin (A-1) is from 1% to 50% by mass.

[0020] In one embodiment of the present invention, when the total amount of pigment (B) is 100 parts by mass, the ratio of black particles (B-1) to hollow particles (B-2) is 85:15 to 15:85.

[0021] In one embodiment of the present invention, when the total content of pigment (B) is 100 parts by mass, the ratio of black particles (B-1) to hollow particles (B-2) is 50:50 to 20:80.

[0022] In one embodiment of the present invention, the initiator (D) includes a photoinitiator and a thermal polymerization initiator.

[0023] In one embodiment of the present invention, the monomer (C) includes a monomer having at least one reactive functional group.

[0024] In one embodiment of the present invention, the total amount of the black opaque photosensitive resin composition used is 100 parts by weight, the amount of resin (A) used is 6 to 13 parts by weight, the amount of pigment (B) used is 6 to 11 parts by weight, the amount of monomer (C) used is 0.5 to 3.5 parts by weight, the amount of initiator (D) used is 0.1 to 2.0 parts by weight, and the amount of solvent (E) used is 70 to 85 parts by weight.

[0025] In one embodiment of the present invention, the resin (A-2) having vinyl unsaturated functional groups includes (meth)acrylic resins.

[0026] In one embodiment of the present invention, the (meth)acrylic resin is composed of (meth)acrylic acid, alkyl (meth)acrylic acid, hydroxyl-containing (meth)acrylic acid, ether-containing (meth)acrylic acid, or alicyclic (meth)acrylic acid.

[0027] The black matrix of the present invention is used between display components and is formed from the aforementioned black light-blocking photosensitive resin composition.

[0028] The black light-shielding film of the present invention is used between display components and is formed from the aforementioned black light-shielding photosensitive resin composition.

[0029] The bezel of the present invention, used between display components, is formed of the aforementioned black light-blocking photosensitive resin composition.

[0030] The filling material of the splicing area of ​​the present invention is used between display components and is formed from the above-mentioned black light-blocking photosensitive resin composition.

[0031] Based on the above, the black light-blocking photosensitive resin composition of the present invention contains both epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2), thus exhibiting excellent matting properties. Furthermore, the black light-blocking photosensitive resin composition of the present invention employs both black particles (B-1) and hollow particles (B-2), thereby reducing reflection and producing matting characteristics. On the other hand, the black light-blocking photosensitive resin composition of the present invention preferably uses hollow particles (B-2) with a particle size variation coefficient (CV) greater than 1 to achieve a better low-reflection effect. Attached Figure Description

[0032] none Detailed Implementation

[0033] The embodiments of the present invention will now be described in detail. However, these embodiments are illustrative, and the present invention is not limited thereto.

[0034] In this document, the range expressed as "from one value to another" is a concise way of representing a range to avoid listing all the values ​​in that range in the specification. Therefore, the description of a particular range of values ​​encompasses any value within that range as well as the smaller range of values ​​defined by that value, just as the arbitrary value and the smaller range of values ​​would be written in the explanatory text of the specification.

[0035] It should be noted that the following uses (meth)acrylic acid to represent acrylic acid and / or methacrylic acid, and (meth)acrylate to represent acrylate and / or methacrylate.

[0036] <Black opaque photosensitive resin composition>

[0037] This invention provides a black, light-blocking, photosensitive resin composition, comprising resin (A), pigment (B), monomer (C), initiator (D), and solvent (E). The various components will be described in detail below.

[0038] Resin (A)

[0039] Resin (A) includes epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2).

[0040] Epoxy Resin (A-1)

[0041] The epoxy resin (A-1) may include compounds represented by formula (1), formula (2), formula (3), formula (4) or formula (5) below.

[0042] Equation (1),

[0043] Equation (2),

[0044] Equation (3),

[0045] Equation (4),

[0046] Equation (5),

[0047] In formulas (1), (2), (3), (4) and (5), R, R', and R'' are each independently at least one substituted cycloalkyl, phenyl, naphthyl, biphenyl, or adamantane.

[0048] More specifically, the epoxy resin (A-1) may include alicyclic epoxy resin of formula (1), linear aliphatic epoxy resin of formula (2), glycidyl ether epoxy resin of formula (3), glycidyl ester epoxy resin of formula (4) or glycidyl amine epoxy resin of formula (5).

[0049] The alicyclic epoxy resin of formula (1) is composed of cyclohexene oxide group, tricyclodecene oxide group, and cyclopentene oxide group. Compounds such as those in the oxide group are representative examples, including: vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, methyl 3,4-epoxycyclohexanecarboxylate (3',4'-epoxycyclohexane), octyl 3,4-epoxycyclohexanecarboxylate (3',4'-epoxycyclohexane), 1-methyl-4-(2-methylepoxyethoxy)-7-oxabicyclo[4.1.0]heptane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate, bis(3,4-epoxycyclohexylmethylene) adipate, or bis(2-methyl-4,5-epoxycyclohexylmethylene) adipate.

[0050] In the molecular structure of the linear aliphatic epoxy resin of formula (2), the main components are aliphatic chains and epoxy groups.

[0051] Specific examples of glycidyl ether epoxy resins of formula (3) may include: bisphenol A type epoxy resin (e.g., “jER1001” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, phenolic varnish type epoxy resin, phenolic varnish type epoxy resin (ortho-, meta-, and p-cresol phenolic varnish type epoxy resins), biphenyl glycidyl ether phenolic epoxy resin, triphenol methane type epoxy resin, ethylene glycol or polyethylene glycol type epoxy resin, propylene glycol or polypropylene glycol type epoxy resin, naphthalene glycol type epoxy resin, isocyanate modified epoxy resin, dicyclopentadiene skeleton type epoxy resin (e.g., “jHP-7200L” manufactured by DIC Corporation), its positional isomers or substitutes having substituents such as alkyl or halogen atoms.

[0052] Specific examples of glycidyl ester epoxy resins of formula (4) may include: diglycidyl phthalate, (methyl)tetrahydrodiglycidyl phthalate, (methyl)hexahydrodiglycidyl phthalate, diglycidyl isophthalate, diglycidyl dimeric acid, or various isomers thereof.

[0053] Specific examples of glycidylamine epoxy resins of formula (5) may include: tetraglycidyl diamino diphenylmethane, diglycidyl aniline or tetraglycidyl phenyl dimethylamine, etc.

[0054] The epoxy resin (A-1) preferably includes compounds represented by formula (6) or formula (7) below.

[0055] Equation (6),

[0056] In equation (6), R 1 This indicates a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group, where n is an integer from 1 to 10.

[0057] Equation (7),

[0058] In equation (7), m is an integer from 1 to 10.

[0059] Resins with vinyl unsaturated functional groups (A-2)

[0060] The resin with vinyl unsaturated functional groups (A-2) includes at least one vinyl unsaturated functional group. The resin with vinyl unsaturated functional groups (A-2) may include (meth)acrylic resins. For example, (meth)acrylic resins may be composed of (meth)acrylic acid, alkyl (meth)acrylates, hydroxyl-containing (meth)acrylates, ether-containing (meth)acrylates, alicyclic (meth)acrylates, or other suitable monomers.

[0061] Alkyl methacrylates may include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tributyl methacrylate, benzyl methacrylate, lauryl methacrylate, or other suitable alkyl methacrylates.

[0062] Hydroxyl-containing (meth)acrylates may include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or other suitable hydroxyl-containing (meth)acrylates.

[0063] Ether-containing (meth)acrylates may include ethoxyethyl (meth)acrylate, glycidyl (meth)acrylate, or other suitable ether-containing (meth)acrylates.

[0064] Alicyclic (meth)acrylates may include cyclohexyl (meth)acrylate, isophorone (meth)acrylate, dicyclopentadienyl (meth)acrylate, or other suitable alicyclic (meth)acrylates.

[0065] The total amount of the black opaque photosensitive resin composition used is 100 parts by weight, and the amount of resin (A) used is 6 to 13 parts by weight. When the total amount of resin (A) is 100% by mass, the content of epoxy resin (A-1) is 1% to 50% by mass.

[0066] The black opaque photosensitive resin composition contains both epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2), thus exhibiting excellent matting properties. If only epoxy resin (A-1) or resin with vinyl unsaturated functional groups (A-2) is used, the uniform cross-linking reaction will easily result in a flat, glossy structure, failing to achieve good matting properties.

[0067] Pigment (B)

[0068] Pigment (B) includes black particles (B-1) and hollow particles (B-2).

[0069] Black particles (B-1) include carbon black, titanium black, organic black pigments, or combinations thereof.

[0070] The hollow particles (B-2) are made of silicon dioxide. The coefficient of variation (CV) of the hollow particles (B-2) is greater than 1, and the particle size ranges from 1 nm to 1000 nm. When hollow particles (B-2) with a CV value greater than 1 are used in the composition of the black opaque photosensitive resin, the distribution is more even and widespread, achieving a better low-reflection effect. If hollow particles with a CV value less than 1 are used, the particle size distribution is more concentrated, and a low-reflection effect cannot be achieved.

[0071] The total amount of the black opaque photosensitive resin composition used is 100 parts by weight, and the amount of pigment (B) used is 6 to 11 parts by weight. When the total amount of pigment (B) is 100 parts by weight, the ratio of black particles (B-1) to hollow particles (B-2) is 85:15 to 15:85, preferably 50:50 to 20:80.

[0072] The black particles (B-1) in the black opaque photosensitive resin composition function to absorb light and reduce reflection. The hollow particles (B-2) in the black opaque photosensitive resin composition function to scatter light and increase light transmittance into the opaque material where they are absorbed by the black body. This reduces light reflection and increases scattering ability, resulting in extinction properties. The black opaque photosensitive resin composition of this invention uses both black particles (B-1) and hollow particles (B-2), thus reducing reflection and producing extinction properties. If the black opaque photosensitive resin composition does not use hollow particles (B-2) in combination with black particles (B-1), but instead uses solid silicon spheres, although the surface can exhibit extinction properties, it suffers from the disadvantage of a whiter black hue and higher reflectivity.

[0073] Monomer (C)

[0074] Monomer (C) includes monomers having at least one reactive functional group. Monomers containing reactive functional groups may include at least one from the group consisting of (meth)acrylate monomers, vinyl monomers, vinyl ether monomers, and epoxy monomers. Monomer (C) may be used alone or in combination with other monomers.

[0075] (Meth)acrylate monomers may include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tributyl (meth)acrylate, isobutyl (meth)acrylate, ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, etc. Butoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, octafluoropentyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol (meth)acrylate 1,4-Butanediol (meth)acrylate, 1,4-Butanediol (meth)acrylate, (meth)acryloylmorpholine, 1,6-Hexanediol (meth)acrylate, polyethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, 1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin, 3-methylpentanediol (meth)acrylate, α,ω-Diacryloylbis(diethylene glycol) phthalate, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate ethoxylate, tri(meth)acrylate of trihydroxyethyl isocyanurate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide and / or propylene oxide adducts of the above-mentioned hydroxyl-containing (meth)acrylates.

[0076] Vinyl monomers may include: (meth)acrylic acid, maleic acid (anhydride), monoalkyl maleate, fumaric acid, monoalkyl fumarate, butenoic acid, itaconic acid, monoalkyl itaconic acid, itaconic acid glycol monoether, citraconic acid, monoalkyl citraconic acid, hexadecyl (meth)acrylate, cinnamic acid, hydroxystyrene, N-hydroxymethyl (meth)acrylamide, and hydroxyethyl (meth)acrylate. (meth)acrylate, HEMA), hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)allyl alcohol, crotonol, isocrotol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethylpropene ether (2-propenoxyethanol), 16-hydroxyhexadecyl methacrylate, sucrose allyl ether, di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, diglycerol tri(meth)acrylate, sorbitan tri(meth)acrylate, di-quaternaryl methacrylate Pentylenetetroxide penta(meth)acrylate, tetraglycerol penta(meth)acrylate, diglycerol di(meth)allyl ether, trimethylolpropane di(meth)allyl ether, pentaerythritol tri(meth)allyl ether, diglycerol tri(meth)allyl ether, sorbitan tri(meth)allyl ether, dipentaerythritol penta(meth)allyl ether, tetraglycerol penta(meth)allyl ether, aminoethyl methacrylate, aminoisopropyl methacrylate, aminobutyl methacrylate, aminohexyl methacrylate, N-aminoethyl(meth)acrylamide, (meth)allylamine, crotonylamine, aminostyrene, methyl α-acetamide acrylate, N-allylphenyl diamine or 16-methacryloylhexadecylamine.

[0077] Vinyl ether monomers may include: diethylene glycol diethylene ether, ethylene glycol monoethylene ether, diethylene glycol diethylene ether, triethylene glycol monoethylene ether, triethylene glycol diethylene ether, propylene glycol diethylene ether, dipropylene glycol diethylene ether, butanediethylene glycol diethylene ether, hexanediethylene glycol diethylene ether, cyclohexanediethanol diethylene ether, hydroxyethyl monoethylene ether, hydroxynonyl monoethylene ether, trimethylolpropane triethylene ether, etc., as well as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanediethanol monoethylene ether, n-propyl vinyl ether, isopropyl vinyl ether, dodecyl vinyl ether, diethylene glycol monoethylene ether, octadecyl vinyl ether, etc., monoethylene ether compounds, etc.

[0078] Epoxy monomers may include: diglycidyl ethers of bisphenols such as biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrachlorobisphenol A, and tetrabromobisphenol A; polyglycidyl ethers of phenolic varnish resins such as phenol-formaldehyde varnish, cresol-formaldehyde varnish, brominated phenol-formaldehyde varnish, and o-cresol-formaldehyde varnish; and ethylene oxides of ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1,4-cyclohexanediol, and bisphenol A. Diglycidyl ethers of alkyl diols, such as bisphenol A propylene oxide adducts and sorbitol polyglycidyl ethers, tris(2,3-epoxypropyl) isocyanurate, triglycidyl tris(2-hydroxyethyl) isocyanurate, glycidyl esters of hexahydrophthalic acid or diglycidyl esters of dimer acids, etc.; 3,4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester (trade name Celloxide manufactured by Daicel). 2021P), 3',4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl ethyl ester, 3',4'-epoxy-6'-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl ester, vinylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spirocyclic-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipic acid, bis(3,4-epoxycyclohexylmethyl) adipic acid, lactone-modified 3',4'-epoxycyclohexyl Alicyclic epoxy compounds such as 3,4-epoxycyclohexyl methyl hexanecarboxylate, methylene bis(3,4-epoxycyclohexane), ethylenedi(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, tetra(3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis(3,4-epoxycyclohexylmethyl)-4,5-epoxytetrahydrophthalic acid ester, 1,2:8,9-diepoxylimonene, and bis(3,4-epoxycyclohexyl)diethylsiloxane.

[0079] The monomer (C) is preferably selected from at least one of the group consisting of compounds represented by formulas (C-1) to (C-4) below.

[0080] Equation (C-1)

[0081] Equation (C-2)

[0082] Equation (C-3)

[0083] Equation (C-4).

[0084] The total amount of the black opaque photosensitive resin composition used is 100 parts by weight, and the amount of monomer (C) used is 0.5 to 3.5 parts by weight.

[0085] The role of monomer (C) in the black opaque photosensitive resin composition is to participate in the polymerization reaction, enabling it to form a film with a high cross-linking density.

[0086] Initiator (D)

[0087] Initiators (D) include photoinitiators and thermal polymerization initiators.

[0088] The photoinitiator includes at least one selected from the group consisting of oxime ester derivatives (oxime ester compounds), triazine compounds, acetophenone compounds, diphenyl ketone compounds, diimidazole compounds, thioxanthone compounds, quinone compounds, acylphosphine oxides, and acyl oxime compounds, preferably oxime ester derivatives (oxime ester compounds).

[0089] Examples of preferred oxime compounds include: 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, or 2-ethoxypropoxyimino-1-phenylpropane-1-one, etc.

[0090] It can also be combined with oxime ester compounds with a diphenyl sulfide skeleton. Oxime ester compounds with a diphenyl sulfide skeleton can be commercially available products, such as Irgacure® OXE01 (manufactured by BASF), Irgacure® OXE04 (manufactured by BASF), NCI-730 (manufactured by ADEKA Corporation), NCI-930 (manufactured by ADEKA Corporation), etc., but are not limited to these.

[0091] It can also be combined with oxime ester compounds with a carbazole skeleton. Oxime ester compounds with a carbazole skeleton can be commercially available products, such as Irgacure® OXE02 (manufactured by BASF), Irgacure® OXE03 (manufactured by BASF), NCI-1919 (manufactured by ADEKA Corporation), NCI-831 (manufactured by ADEKA Corporation), etc., but are not limited to these.

[0092] Triazine compounds may include chemcure-PAG-1 (trade name; manufactured by Heng Chiao Industrial Co., Ltd.), chemcure-PAG-2 (trade name; manufactured by Heng Chiao Industrial Co., Ltd.), or other suitable triazine compounds. Triazine compounds may be used alone or in combination.

[0093] Acetophenone compounds may include Irgacure 907, 369E (trade name; manufactured by BASF), Chemcure-96 (trade name; manufactured by Hengqiao Industry Co., Ltd.), or other suitable acetophenone compounds. Acetophenone compounds may be used alone or in combination.

[0094] Diphenyl ketone compounds may include chemcure-BP, chemcure-64 (trade name; manufactured by Heng Chiao Industrial Co., Ltd.), or other suitable diphenyl ketone compounds. A single diphenyl ketone compound may be used alone, or multiple compounds may be used in combination.

[0095] Diimidazole compounds may include Chemcure-BCIM, Chemcure-TCDM (trade name; manufactured by Heng Chiao Industrial Co., Ltd.), or other suitable diimidazole compounds. A single diimidazole compound may be used alone, or multiple compounds may be used in combination.

[0096] Thioxanthone compounds may include Irgacure ITX (trade name; manufactured by BASF) or other suitable thioxanthone compounds. Thioxanthone compounds may be used alone or in combination.

[0097] Suitable quinone compounds can be selected. Quinone compounds can be used alone or in combination.

[0098] Acylphosphine oxides may include Irgacure TPO, Irgacure 819 (trade name; manufactured by BASF) or other suitable acylphosphine oxides. Acylphosphine oxides may be used alone or in combination.

[0099] Acyloxime compounds may include any suitable acyloxime compounds. Acyloxime compounds may be used alone or in combination.

[0100] Thermal polymerization initiators may include azo compounds such as 2,2”-azobisisobutyronitrile (AIBN), 3-propionitrile, azobismalonitrile, and dimethyl-(2,2”)-azobis(2-methylpropionate), organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate, and antimony hexafluoride or ammonium salt compounds.

[0101] The total amount of the black opaque photosensitive resin composition used is 100 parts by weight, and the amount of the initiator (D) used is 0.1 to 2.0 parts by weight.

[0102] The function of the initiator (D) in the black opaque photosensitive resin composition is to generate free radicals to initiate the polymerization reaction during the exposure process, and to work in conjunction with the thermal polymerization initiator to ensure the complete crosslinking reaction.

[0103] Solvent (E)

[0104] Solvents (E) may include propylene glycol methyl ether acetate (PGMEA) and other high-boiling solvents: ethyl 3-ethoxypropionate (EEP), ethyl pyruvate (PE), ethyl lactate, butyl lactate, benzyl alcohol, 3-methoxybutyl acetate (MBA), 3-methoxy-3-methylbutanol, 1,4-butanediol diacrylate (BDDA), γ-butyrolactone, or propylene glycol monobutyl ether; high-surface solvents: γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide (DMSO), BGC, EDG; or low-boiling solvents: methyl isopentyl ketone, methyl ethyl ketone, isopropanol, etc.

[0105] The total amount of the black opaque photosensitive resin composition used is 100 parts by weight, and the amount of solvent (E) used is 70 to 85 parts by weight.

[0106] The role of the solvent (E) is to give the black opaque photosensitive resin composition an appropriate viscosity that can accommodate variations in different coating processes.

[0107] <Preparation Method of Black Opaque Photosensitive Resin Composition>

[0108] There are no particular limitations on the preparation method of the black opaque photosensitive resin composition. For example, resin (A), pigment (B), monomer (C), initiator (D), and solvent (E) are placed in a stirrer and stirred until they are mixed evenly to obtain a liquid black opaque photosensitive resin composition.

[0109] <Manufacturing Method of Black Light-Shielding Material>

[0110] An exemplary embodiment of the present invention provides a black light-shielding material formed using the above-described black light-shielding photosensitive resin composition. The black light-shielding material may include a black matrix, a black light-shielding film, a border, or a filler material for splicing areas, used between display components.

[0111] A black, light-blocking, photosensitive resin composition was coated onto a substrate, and excess solvent was removed by evacuation to a pressure of 133 Pa. Afterward, it was placed on a heated plate at 100°C for pre-bake for 5 to 10 minutes to form a thin film. Next, a high-pressure mercury lamp at 100 mJ / cm² was used. 2 Up to 300mJ / cm 2 The material is exposed to a certain amount of light. After exposure, it is placed in an oven at 150°C for 10 to 30 minutes to obtain a black light-blocking material. The obtained black light-blocking material can be a film with a thickness of 3.0 µm to 6.0 µm.

[0112] The substrate can be a glass substrate, a plastic substrate material (such as a polyethersulfone (PES) board, a polycarbonate (PC) board, or a polyimide (PI) film) or other light-transmitting substrate, and there are no particular restrictions on its type.

[0113] There are no particular restrictions on the coating method, but spraying, roller coating, spin coating or similar methods can be used, and generally speaking, spin coating is widely used.

[0114] The invention will be described in detail below with reference to examples. The following examples are provided to illustrate the invention, and the scope of the invention includes the scope described in the following claims, as well as their substitutions and modifications, but is not limited to the scope of the examples.

[0115] Examples of black light-blocking photosensitive resin composition and black light-blocking material

[0116] Examples 1 to 11 and Comparative Examples 1 to 8 are described below as examples of black light-blocking photosensitive resin composition and black light-blocking material.

[0117] Example 1

[0118] a. Black, light-blocking, photosensitive resin composition

[0119] Two parts by weight of HP-7200L (manufactured by DIC Corporation), eight parts by weight of resin A-4 as shown in Table 1, 7.1 parts by weight of Black carbon black paste (manufactured by Tokushiki Corporation), 1.3 parts by weight of Hollow Silica dispersion (manufactured by Sanyo Pigment Co., Ltd., particle size 54 nm ± 82 nm, particle size distribution 2 nm to 450 nm), 0.45 parts by weight of DPHA, 0.45 parts by weight of monomer C-3 as shown in Table 1, 0.35 parts by weight of Irgacure® OXE03 (manufactured by BASF), and 0.35 parts by weight of initiator D-3 as shown in Table 1 were added to 80 parts by weight of propylene glycol methyl ether acetate PGMEA and stirred evenly with a stirrer to obtain the black light-blocking photosensitive resin composition of Example 1.

[0120] b. Light conversion layer

[0121] The resin compositions prepared in the examples were coated onto a glass substrate using spin coating / spray coating methods. Excess solvent was removed by evacuation and depressurization to 133 Pa. Next, the substrate was placed on a heated plate at 100°C for pre-bake for 5 to 10 minutes to form a thin film. Then, the film was subjected to a high-pressure mercury lamp (ELS106SA) containing gamma, h, and i rays at 100 mJ / cm². 2 Up to 300mJ / cm 2 The material was exposed to a certain amount of light. After exposure, it was placed in an oven at 150°C and post-baked for 10 to 30 minutes to obtain a black light-blocking material. The obtained black light-blocking material can be a thin film with a thickness of 3.0 µm to 6.0 µm. The obtained black light-blocking material was evaluated using the following evaluation methods, and the results are shown in Table 3.

[0122] Examples 2 to 11 and Comparative Examples 1 to 8

[0123] The black opaque photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 8 were prepared using the same steps as in Example 1, except that the types and amounts of components in the black opaque photosensitive resin compositions were changed (as shown in Table 2), where the components / compounds corresponding to the numbers in Table 2 are shown in Table 1. The obtained black opaque photosensitive resin compositions were made into black opaque materials and evaluated using the following evaluation methods, and the results are shown in Table 3.

[0124] [Table 1]

[0125]

[0126] [Table 2]

[0127]

[0128] [Table 2] (continued)

[0129]

[0130] <Measurement Methods and Calculation Formulas>

[0131] a. Methods for measuring reflectance and calculating scattering ratio

[0132] The SCI (Specular Component Included) and SCE (Specular Component Excluded) of the black light-blocking material were measured using a spectrophotometer (Konica Minolta 2600d) with a viewing angle of 10° and a light source of D65.

[0133] The scattering ratio (%) is calculated according to the following formula:

[0134]

[0135] b. Methods for determining L* value

[0136] The L* value of the black light-blocking material was measured using a spectrophotometer (Konica Minolta 2600d) with a viewing angle of 10° and a light source of D65.

[0137] c. Methods for determining OD values

[0138] The light-blocking OD value of the black film was measured using a density meter (X-rite 361C).

[0139] d. Calculation method of CV (coefficient of variation) value

[0140] The CV (coefficient of variation) value refers to the coefficient of variation (also known as the relative standard deviation) of the particle size distribution of transparent particles. This value is used to represent the degree of diffusion (error in particle size) relative to the average value (arithmetic mean diameter), and is calculated as follows. The smaller the CV value, the narrower (steeper) the particle size distribution; the larger the CV value, the wider (flatter) the particle size distribution.

[0141]

[0142] [Table 3]

[0143]

[0144] [Table 3] (continued)

[0145]

[0146] <Evaluation Results>

[0147] As shown in Tables 2 and 3, compared to Comparative Examples 7 and 8, Comparative Examples 1 to 6 and Examples 1 to 7 contain both epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2). Therefore, the scattering ratio of the matting effect is above 85%, and even better, it can meet the requirement of greater than 90%, which shows good matting effect. However, Comparative Examples 1 and 2 only used black particles (B-1) without hollow particles (B-2), while Comparative Example 3 used black particles (B-1) with solid silicon spheres. Therefore, although the surface has matting effect, the black color appears whiter and the reflectivity is higher, which cannot achieve the effect of L*<20 and SCI, SCE<3.

[0148] On the other hand, in Examples 1 to 11, the particle size of the added hollow particles (B-2) had a particle size distribution variation coefficient (CV) greater than 1, indicating a relatively even and widespread distribution, resulting in better low reflectivity and L* performance. Compared to Comparative Examples 4 to 6, Examples 8 and 9, although also containing a mixture of epoxy resin (A-1) and a resin with vinyl unsaturated functional groups (A-2) and added hollow particles, had a more concentrated particle size distribution (particle size distribution variation coefficient (CV) less than 1) in Comparative Examples 4 to 6. Therefore, their SCI and SCE were too high, failing to achieve a low reflectivity effect.

[0149] Examples 10 and 11 combine black particles of different morphologies (B-1) with hollow particles (B-2) with a particle size distribution variation coefficient (CV) greater than 1. Both combinations exhibit good low reflectivity and good light-blocking properties (OD>3). The ratio of black particles (B-1) to hollow particles (B-2) can be 85:15 to 15:85.

[0150] As for Comparative Examples 7 and 8, although hollow particles with a particle size distribution variation coefficient (CV) greater than 1 (B-2) were also used, only epoxy resin (A-1) or resin with ethylene unsaturated functional groups (A-2) were used. Because the crosslinking reactivity was uniform, it was easy to form a flat and glossy structure. The scattering ratio was much less than 90%, and good extinction properties could not be achieved.

[0151] In summary, the black light-blocking photosensitive resin composition of the present invention contains both epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2), thus exhibiting excellent anti-reflection properties. Furthermore, the black light-blocking photosensitive resin composition of the present invention employs both black particles (B-1) and hollow particles (B-2), thereby reducing reflection and producing extinction properties. The black particles (B-1) in the black light-blocking photosensitive resin composition absorb light and reduce reflection. The hollow particles (B-2) in the black light-blocking photosensitive resin composition scatter light and increase light transmittance into the light-blocking material where they are absorbed by the black body. This reduces light reflection and increases scattering ability, producing extinction properties. On the other hand, the black light-blocking photosensitive resin composition of the present invention preferably uses hollow particles (B-2) with a particle size variation coefficient (CV) greater than 1, resulting in a more even and widespread distribution, to achieve a better low-reflection effect.

[0152] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A black, light-blocking, photosensitive resin composition, characterized in that, include: Resin (A), including epoxy resin (A-1) and resin with vinyl unsaturated functional groups (A-2). Pigment (B), including black particles (B-1) and hollow particles (B-2); Monomer (C) includes monomers having at least one reactive functional group; Initiator (D); and Solvent (E) The epoxy resin (A-1) described herein comprises a compound represented by the following formula (3). Equation (3), In formula (3), R is at least one substituted cycloalkyl, phenyl, naphthyl, biphenyl, or adamantane. The particle size variation coefficient (CV) of the hollow particles (B-2) is greater than 1.

2. The black opaque photosensitive resin composition according to claim 1, characterized in that, The epoxy resin (A-1) comprises compounds represented by formula (6) or formula (7) below. Equation (6), In equation (6), R 1 This indicates a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group, where n is an integer from 1 to 10. Equation (7), In equation (7), m is an integer from 1 to 10.

3. The black opaque photosensitive resin composition according to claim 1, characterized in that, The black particles (B-1) include carbon black, titanium black, organic black pigments, or combinations thereof.

4. The black opaque photosensitive resin composition according to claim 1, characterized in that, The hollow particles (B-2) are made of silicon dioxide.

5. The black opaque photosensitive resin composition according to claim 1, characterized in that, The hollow particles (B-2) have a particle size range of 1 nm to 1000 nm.

6. The black opaque photosensitive resin composition according to claim 1, characterized in that, When the total amount of resin (A) is 100% by mass, the content of epoxy resin (A-1) is from 1% to 50% by mass.

7. The black opaque photosensitive resin composition according to claim 1, characterized in that, When the total amount of pigment (B) is 100 parts by mass, the ratio of black particles (B-1) to hollow particles (B-2) is 85:15 to 15:

85.

8. The black opaque photosensitive resin composition according to claim 7, characterized in that, When the total content of the pigment (B) is 100 parts by mass, the ratio of the black particles (B-1) to the hollow particles (B-2) is 50:50 to 20:

80.

9. The black opaque photosensitive resin composition according to claim 1, characterized in that, The initiator (D) includes photoinitiators and thermal polymerization initiators.

10. The black opaque photosensitive resin composition according to claim 1, characterized in that, Based on the total amount of the black opaque photosensitive resin composition used being 100 parts by mass, the amount of resin (A) used is 6 to 13 parts by mass, the amount of pigment (B) used is 6 to 11 parts by mass, the amount of monomer (C) used is 0.5 to 3.5 parts by mass, the amount of initiator (D) used is 0.1 to 2.0 parts by mass, and the amount of solvent (E) used is 70 to 85 parts by mass.

11. The black opaque photosensitive resin composition according to claim 1, characterized in that, The resin (A-2) with vinyl unsaturated functional groups includes (meth)acrylic resins.

12. The black opaque photosensitive resin composition according to claim 11, characterized in that, The (meth)acrylic resin is composed of (meth)acrylic acid, alkyl (meth)acrylic acid, hydroxyl-containing (meth)acrylic acid, ether-containing (meth)acrylic acid, or alicyclic (meth)acrylic acid.

13. A black matrix, characterized in that, For use between display components, formed of a black light-shielding photosensitive resin composition according to any one of claims 1 to 12.

14. A black light-blocking film, characterized in that, For use between display components, formed of a black light-shielding photosensitive resin composition according to any one of claims 1 to 12.

15. A frame, characterized in that, For use between display components, formed of a black light-shielding photosensitive resin composition according to any one of claims 1 to 12.

16. A filling material for splicing areas, characterized in that, For use between display components, formed of a black light-shielding photosensitive resin composition according to any one of claims 1 to 12.

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