Colored photosensitive resin composition, and optical element and display device using the same

Abstract

A colored photosensitive resin composition, and an optical element and display device using the same. The colored photosensitive resin composition includes a photopolymerization initiator, a black colorant, a resin, a photopolymerizable monomer, and a solvent. The optical absorption spectrum of the photopolymerization initiator in the wavelength range of 350 nm to 380 nm overlaps with the exposure optical spectrum of a mercury lamp exposure system in an area of ​​100 to 700 nm.

Description

Technical Field

[0001] The invention relates to a colored photosensitive resin composition, and an optical element and a display device using the same. Background Art

[0002] In display technology, a colored photosensitive resin composition can be used to form a color filter that controls the color of each pixel. The colored photosensitive resin composition can also be used to form a partition wall structure of a display panel. The method for manufacturing the partition wall structure includes exposing and developing the colored photosensitive resin composition to define a pattern. For example, the partition wall structure can be applied to a quantum dot display (QD) to separate the various light-emitting units (such as micro light-emitting diode (micro LED) chips) from each other. The properties of the colored photosensitive resin composition and the optical elements formed using it (such as color filters, partition wall structures, etc.) are related to the quality of the display product. However, the black photosensitive resin composition has a strong phototropism, so there is often a problem of incomplete photosensitivity during the exposure reaction, which indirectly leads to problems such as reliability or peeling of the black photosensitive resin composition or the black optical elements formed using it. Summary of the Invention

[0003] The present invention relates to a colored photosensitive resin composition, and an optical element and a display device using the same, which have excellent reliability quality.

[0004] According to one aspect of the present invention, a colored photosensitive resin composition is provided, comprising a photopolymerization initiator, a black colorant, a resin, a photopolymerizable monomer, and a solvent. The optical absorption spectrum of the photopolymerization initiator in the wavelength range of 350 nm to 380 nm overlaps with the exposure optical spectrum of a mercury lamp exposure system by an area of ​​100 to 700 nm.

[0005] According to another aspect of the present invention, an optical element is provided. The optical element is formed from the colored photosensitive resin composition.

[0006] According to yet another aspect of the present invention, a display device is provided, comprising the above-mentioned optical element.

[0007] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but this does not limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 Displays the spectrum of the photopolymerization initiator and the exposure machine, as well as the overlapping area between the two spectra. DETAILED DESCRIPTION

[0009] The structural principle and working principle of the present invention are described in detail below with reference to the accompanying drawings:

[0010] The present invention relates to a colored photosensitive resin composition, and an optical element and a display device using the same. The colored photosensitive resin composition of the embodiment has good reliability quality.

[0011] In an embodiment, the colored photosensitive resin composition includes a photopolymerization initiator. The overlap area between the optical absorption spectrum of the colored photosensitive resin composition's photopolymerization initiator in the wavelength range of 350 nm to 380 nm and the exposure optical spectrum of a mercury lamp exposure machine is 100 to 700 Å, for example, 150 to 700 Å. As a result, an optical element (black optical element) formed from the colored photosensitive resin composition (black photosensitive resin composition) can have good reliability and quality. The optical absorption spectrum of the photopolymerization initiator (photopolymerization initiator spectrum) is measured using a spectrometer with a wavelength range of 200 nm to 600 nm. The measured data is then normalized based on the maximum value, and the normalized data is plotted. The exposure optical spectrum diagram (exposure machine spectrum diagram) of a mercury lamp exposure machine is obtained by measuring the exposure optical spectrum of the mercury lamp exposure machine's light source (i-Line, peak wavelength 365nm) using an optical spectrometer. The measured data is normalized at its maximum value and the resulting normalized data is plotted.

[0012] The photopolymerization initiator may account for 1 wt % to 10 wt % of the colored photosensitive resin composition.

[0013] In an embodiment, the photopolymerization initiator may include an acetophenone-based photoinitiator, an OXIME-based photoinitiator, or a combination thereof.

[0014] In one embodiment, the photopolymerization initiator may have one of the following chemical formulas.

[0015]

[0016]

[0017] According to an embodiment, the colored photosensitive resin composition is a black photosensitive resin composition including a black colorant.

[0018] The black colorant may account for 1 wt % to 30 wt % of the colored photosensitive resin composition.

[0019] Black colorants include colorant compositions capable of producing a black coloring effect. Black colorants (or colorant compositions capable of producing a black coloring effect) may include pigments and / or dyes. Black colorants (or colorant compositions capable of producing a black coloring effect) may include black pigments and / or black dyes. Black pigments may include carbon black pigments, etc. Colorant compositions capable of producing a black coloring effect may include violet colorants, blue colorants, and yellow colorants and / or orange colorants. Yellow colorants may include yellow pigments and / or yellow dyes. Yellow pigments may include CI Pigment Yellow 138, etc. Orange colorants may include orange pigments and / or orange dyes. Orange pigments may include CI Pigment Orange 64, etc. Blue colorants may include blue pigments and / or blue dyes. Blue pigments may include CI Pigment Blue 15:6, etc. Purple colorants may include violet pigments and / or violet dyes. Violet pigments may include CI Pigment Violet 29, etc. Violet dyes may include oxanthone dyes, etc. In one embodiment, the colorant composition of the black colorant is composed of 10 wt% to 40 wt% of CI Pigment Yellow 138, 10 wt% to 40 wt% of CI Pigment Violet 29, 0 wt% to 15 wt% of an oxanthone dye, and 30 wt% to 60 wt% of CI Pigment Blue 15:6. In one embodiment, the colorant composition of the black colorant is composed of 10 wt% to 40 wt% of CI Pigment Orange 64, 10 wt% to 40 wt% of CI Pigment Violet 29, 0 wt% to 15 wt% of an oxanthone dye, and 30 wt% to 60 wt% of CI Pigment Blue 15:6.

[0020] According to some embodiments, the solvent may include, but is not limited to, at least one selected from the group consisting of: ester solvents (herein, a solvent containing -COO- but not -O- in the molecule), ether solvents (herein, a solvent containing -O- but not -COO- in the molecule), ether ester solvents (herein, a solvent containing -COO- and -O- in the molecule), ketone solvents (herein, a solvent containing -CO- but not -COO- in the molecule), alcohol solvents (herein, a solvent containing OH but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. The solvent may include, but is not limited to, propylene glycol methyl ether acetate. Hydrophilic solvents include: dimethyl sulfoxide (DMSO), diethyl sulfoxide, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidon e, NEP), N-propyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol, tetrahydrofuran (THF), dioxane, dioxolane, propylene glycol methyl ether (PGME), tetraethylene glycol dimethyl ether (TGDE), butyl cellosolve, γ-butyrolactone (GBL), xylene, toluene, hexamethylol-2-amide, propylene glycol methyl ether acetate (PGMEA), or a mixture thereof. The boiling point of the solvent may be 150° C. to 230° C., but the present invention is not limited thereto.

[0021] The resin may account for 20 wt % to 80 wt % of the colored photosensitive resin composition.

[0022] The resin may include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, such as (meth)acrylates such as pentaerythritol triacrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate. Examples include itaconic esters in which the (meth)acrylic acid portion of these (meth)acrylates is replaced by itaconic acid, butenoic acid, or maleic acid.

[0023] In one embodiment, the resin has a constituent unit represented by the following chemical formula:

[0024]

[0025] In one embodiment, the resin has a constituent unit represented by the following chemical formula:

[0026]

[0027] The photopolymerizable monomer may account for 10 wt % to 40 wt % of the colored photosensitive resin composition.

[0028] The photopolymerizable monomer may include, but is not limited to, at least one selected from the group consisting of: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and other polymerizable compounds having one ethylenically unsaturated bond; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and other polymerizable compounds having two ethylenically unsaturated bonds; and trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate. , pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexaacrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, four pentaerythritol deca(meth)acrylate, four pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like, a polymerizable compound having three ethylenically unsaturated bonds.

[0029] The colored photosensitive resin composition may further include other additives such as a leveling agent, a surfactant, a leveling agent, a polymerization initiation aid, a filler, an adhesion promoter, an antioxidant, a light stabilizer, etc., but is not limited thereto.

[0030] The leveling agent may account for 0.1 wt % to 2 wt % of the colored photosensitive resin composition.

[0031] Leveling agents are commonly used coating additives that help form a smooth, even film during the drying process. Examples of leveling agents include silicone surfactants, fluorine-based surfactants, and silicone surfactants containing fluorine atoms. These surfactants may have polymerizable groups in their side chains.

[0032] Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specific examples include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names: manufactured by Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)).

[0033] Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Corporation), SURFLON (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

[0034] Examples of the fluorine-containing silicone surfactant include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0035] Another embodiment of the present invention relates to an optical element formed from the colored photosensitive resin composition according to any of the aforementioned embodiments. For example, the colored photosensitive resin composition according to any of the aforementioned embodiments can be formed into the optical element by photolithography, inkjet printing, or printing, but is not limited thereto. The optical element can be a colored or black optical element.

[0036] Yet another embodiment of the present invention relates to a display device, which may include the aforementioned optical element, but is not limited thereto. According to some embodiments, the display device may be a liquid crystal display, an electroluminescent display, or a plasma display, etc. The display device may include a quantum dot display (QD). The optical element may be a color filter or a partition wall structure. The partition wall structure is used to separate individual light-emitting units (e.g., micro light-emitting diode (micro LED) chips) from each other.

[0037] To make the above-mentioned objects, features, and advantages of the present invention more clearly understood, specific examples are given below for detailed explanation:

[0038] Tables 1 and 2 list the black photosensitive resin compositions and analysis results for Examples and Comparative Examples. Tables 1 and 2 show the weight percentages of the components of the black photosensitive resin compositions. The components and analysis methods of the black photosensitive resin compositions are described below.

[0039] [Resin preparation]

[0040] [Resin (C1)]

[0041] 213.6 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred while replacing the atmosphere with nitrogen and then heated to 90°C. Next, 4.0 g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture consisting of 20.0 g (0.20 mol) of methyl methacrylate, 88.0 g (0.40 mol) of tricyclodecyl methacrylate, and 34.4 g (0.4 mol) of methacrylic acid. The mixture was then added dropwise from the dropping funnel to the flask. After the addition was complete, a copolymerization reaction was carried out at 95°C with stirring for 3 hours to produce a copolymer. Next, after the flask was purged with air, 42.6 g (0.3 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibitor) were added, and a ring-opening addition reaction was carried out at 120°C for 6 hours to produce a copolymer. Subsequently, 221.3 g of propylene glycol monomethyl ether was added to the reaction solution to produce a copolymer solution having a solids concentration of 30% by mass (solids acid value 30 mgKOH / g, weight average molecular weight 37,100). The resulting copolymer resin (C1) has the structural units shown in the following Chemical Formula 2.

[0042]

[0043] [Resin (C2)]

[0044] A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was flowed with an appropriate amount of nitrogen gas to create a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed therein and heated to 85°C while stirring. Subsequently, a solution prepared by dissolving 19 parts of methacrylic acid (forming the structural unit on the lower left side) and 171 parts of a mixture of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (containing ratio of 50:50 by molar ratio) (trade name "E-DCPA, manufactured by Daicel Corporation) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 5 hours using a dropping pump. On the other hand, a solution of 26 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 120 parts of propylene glycol monomethyl ether acetate was dripped into the flask using another dripping pump over a period of about 5 hours. After the dripping of the polymerization initiator was completed, the temperature was maintained at the same level for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (C2)) having a solid content of 43.5%. The obtained resin (C2) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value converted to solid content of 53 mg-KOH / g. Resin (C2) has a structural unit as shown in the following chemical formula 3.

[0045]

[0046] [Resin (C3)]

[0047] The atmosphere in a flask equipped with a reflux condenser, dropping funnel, and stirrer was replaced with nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added. The mixture was heated to 80°C while stirring. Next, a mixed solution of 289 parts of a mixture of 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate, and 3,4-epoxytricyclo[5.2.1.02]6)decan-9-yl acrylate (containing ratio of 1:1 by mole) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Separately, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was held at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (C3)) solution having a solids content of 35.1% and a viscosity of 125 mPas as measured with a B-type viscometer (23°C). The resulting copolymer (resin (C3)) had a weight-average molecular weight (Mw) of 9.2 × 10³, a molecular weight distribution (Mw / Mn) of 2.08, and an acid value (based on solids content) of 77 mgKOH / g. Resin (C3) has the structural units shown in Chemical Formula 3.

[0048] [Photopolymerizable monomer]

[0049] Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) was used as the photopolymerizable monomer.

[0050] [Preparation of Photopolymerization Initiator (A)]

[0051] [Photopolymerization initiator (A1)]

[0052] 90 g of diphenyl sulfide, 62 g of methyl chlorooxalyl ester, and 150 mL of dichloromethane were cooled in an ice-water bath at approximately 5°C. Then, 80 g of aluminum trichloride was slowly added portionwise to the reaction system while stirring for two hours. The dichloromethane solution containing the product was poured into ice water with continuous stirring. The dichloromethane layer was washed with deionized water and the dichloromethane product solution was rotary evaporated to obtain a pale yellow solid, Compound a1.

[0053] Stir 81.7 g of compound a1, 100 mL of dichloromethane, and 16.7 g of aluminum chloride in an ice-water bath at approximately 0°C. Then, slowly add 11.9 g of thionyl chloride dropwise to the reaction system until the starting material volume remains constant. Next, slowly add 100 mL of ice-cold deionized water dropwise to the reaction system. The aqueous layer is the aqueous solution of compound a2.

[0054] 19 g of KPF6 solid was added to the aqueous solution of compound a2 for ion exchange. Deionized water was then added with stirring. As the KPF6 solid dissolved, the target product, photopolymerization initiator (A1), gradually precipitated. The product was filtered, recrystallized from methanol, and dried to obtain the photopolymerization initiator (A1) as a white solid. The photopolymerization initiator (A1) has the chemical formula 5.

[0055]

[0056] [Photopolymerization initiator (A2)]:

[0057] 85 g of diphenyl sulfide, 59 g of methyl chlorooxalyl ester, and 150 mL of dichloromethane were cooled in an ice-water bath at approximately 5°C. Then, 75 g of aluminum trichloride was slowly added portionwise to the reaction system while stirring for two hours. The dichloromethane solution containing the product was poured into ice water with continuous stirring. The dichloromethane layer was washed with deionized water and the dichloromethane product solution was rotary evaporated to obtain a pale yellow solid, Compound b1.

[0058] Stir 81.7 g of compound b1, 100 mL of dichloromethane, and 40 g of aluminum chloride in an ice-water bath at approximately 0°C. Then, slowly add 23 g of thionyl chloride dropwise to the reaction mixture until the starting material volume remains constant. Next, slowly add 100 mL of ice-cold deionized water dropwise to the reaction mixture. The aqueous layer is the aqueous solution of compound b2.

[0059] 25 g of KPF6 solid was added to the aqueous solution of compound b2 for ion exchange. Deionized water was then added with stirring. As the KPF6 solid dissolved, the target product, photopolymerization initiator (A2), gradually precipitated. The product was filtered, recrystallized from methanol, and dried to obtain a white solid photopolymerization initiator (A2). Photopolymerization initiator (A2) has the chemical formula 6.

[0060]

[0061] [Photopolymerization initiator (A3)]

[0062] 330 mg of 4,4'-(9-fluorenyl)diphenol, 201 mg of 1-chloroundecane, and 125 mg of 5-chloropentan-1-ol were added to a tetrahydrofuran (THF) solution, stirred, and heated to 70°C. After reacting for one day, the mixture was cooled to room temperature to obtain a solution containing ketone compound 1. 1.2 equivalents (eq.) of ketone compound 1, 1.5 equivalents of a haloalkyl group, 1 eq. of potassium carbonate, and dimethyl sulfoxide (DMSO) were added in an amount equal to five times the theoretical yield. The mixture was heated and stirred at 130°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, ion-exchanged water was added and the precipitated solid was collected by filtration. The mixture was thoroughly washed and dried to obtain ketone compound c2.

[0063] 1.2 equivalents of the obtained ketone body c2, 1.8 equivalents of hydroxylamine hydrochloride, and dimethylformamide (twice the theoretical yield) were added to the mixture under nitrogen atmosphere at 80°C with stirring for 1.5 hours. After cooling to room temperature, the mixture was separated into oil and water using ion-exchanged water. The solvent was removed to obtain photopolymerization initiator (A3). Photopolymerization initiator (A3) has the chemical formula 7.

[0064]

[0065] [Photopolymerization initiator (A4)]

[0066] A suspension of 9 g of phenylnaphthylamine, 10 g of 4-bromobenzophenone, 9 g of sodium tert-pentyloxide, and 1 g of bistriphenylphosphine palladium in 150 mL of toluene was stirred at 100°C for 4.5 hours. After cooling to room temperature, silica gel was added to the reaction solution and stirred for 30 minutes. The mixture was then filtered and the solvent was distilled off at 40°C to obtain Compound d1 as a brown solid.

[0067] To a 150 mL nitromethane solution of compound d1, 6 g of acetyl chloride and 11 g of aluminum chloride were added, and the mixture was stirred at the same temperature for 7 hours. Furthermore, 12 g of acetyl chloride and 20 g of aluminum chloride were added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice-cooled water and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, and the solvent was distilled off at 40°C, followed by crystallization to obtain compound d2 as a cream-colored solid.

[0068] To a 56 mL ethanol solution of compound d2, 2.5 g of hydroxylamine hydrochloride, 3.5 g of sodium acetate, and 30 mL of water were added, and the mixture was stirred under reflux for 4 hours. After cooling to room temperature, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. The solvent was then distilled off at 40°C to obtain compound d3.

[0069] To a 50 mL chloroform solution of compound d3, 4.5 g of triethylamine and 3.5 g of acetyl chloride were added under ice-cooling and stirred at room temperature overnight. Water was added under ice-cooling to separate the oil and water. The organic layer was washed with water and the solvent was distilled off at 40°C to obtain a yellow amorphous photopolymerization initiator (A4). Photopolymerization initiator (A4) has Chemical Formula 8.

[0070]

[0071] [Photopolymerization initiator (A5)]

[0072] A suspension of 9 g of phenylnaphthylamine, 10 g of 4-bromobenzophenone, 9 g of sodium tert-pentyloxide, and 1 g of bistriphenylphosphine palladium in 150 mL of toluene was stirred at 100°C for 4.5 hours. After cooling to room temperature, silica gel was added to the reaction solution and stirred for 30 minutes. The mixture was filtered and the solvent was distilled off at 40°C to obtain Compound e1 as a brown solid.

[0073] To a 150 mL nitromethane solution of compound e1, 5 g of acetyl chloride and 9.5 g of aluminum chloride were added, and the mixture was stirred at the same temperature for 6 hours. Furthermore, 10 g of acetyl chloride and 22 g of aluminum chloride were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into ice-cooled water and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, and the solvent was distilled off at 40°C. Crystallization was then performed to obtain compound e2 as a cream-colored solid.

[0074] To a 60 mL ethanol solution of compound e2, 2 g of hydroxylamine hydrochloride, 3 g of sodium acetate, and 30 mL of water were added, and the mixture was stirred under reflux for 4 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, and the solvent was distilled off at 40°C to obtain compound e3.

[0075] To a 50 mL chloroform solution of compound e3, 4 g of triethylamine and 3.2 g of acetyl chloride were added under ice-cooling and stirred at room temperature overnight. Water was added under ice-cooling to separate the oil and water. The organic layer was washed with water and the solvent was distilled off at 40°C to obtain a yellow amorphous photopolymerization initiator (A5). Photopolymerization initiator (A5) has Chemical Formula 9.

[0076]

[0077] [Photopolymerization initiator (A6)]

[0078] A suspension of 9 g of phenylnaphthylamine, 10 g of 4-bromobenzophenone, 9 g of sodium tert-pentyloxide, and 1 g of bistriphenylphosphine palladium in 150 mL of toluene was stirred at 100°C for 4.5 hours. After cooling to room temperature, silica gel was added to the reaction mixture and stirred for 30 minutes. The mixture was filtered and the solvent was distilled off at 40°C to obtain Compound f1 as a brown solid.

[0079] To a 150 mL nitromethane solution of compound f1, 7.5 g of acetyl chloride and 13 g of aluminum chloride were added, and the mixture was stirred at the same temperature for 6 hours. Furthermore, 13 g of acetyl chloride and 28 g of aluminum chloride were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into ice-cooled water and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, and the solvent was distilled off at 40°C. After crystallization, compound f2 was obtained as a cream-colored solid.

[0080] To a 60 mL ethanol solution of compound f2, 2.8 g of hydroxylamine hydrochloride, 4.1 g of sodium acetate, and 30 mL of water were added, and the mixture was stirred under reflux for 4 hours. After cooling to room temperature, extraction was performed with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was distilled off at 40°C to obtain compound f3.

[0081] To a 50 mL chloroform solution of compound f3, 2.5 g of triethylamine and 2.5 g of acetyl chloride were added under ice-cooling and stirred at room temperature overnight. Water was added under ice-cooling to separate the oil and water. The organic layer was washed with water and the solvent was distilled off at 40°C to obtain a yellow amorphous photopolymerization initiator (A6). Photopolymerization initiator (A6) has Chemical Formula 10.

[0082]

[0083] [Photopolymerization initiator (A7)]

[0084] 1.1 equivalents of ketone body 1, 1.6 equivalents of an alkyl halide, 3.3 equivalents of potassium carbonate, and 4.5 times the theoretical yield of dimethyl sulfoxide were added, and the mixture was heated and stirred at 130°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, ion-exchanged water was added, and the precipitated solid was filtered. The solid was thoroughly washed and dried to obtain ketone body g2.

[0085] 1.5 equivalents of ketone body g2, 2.3 equivalents of hydroxylamine hydrochloride, and 2.2 times the theoretical yield of dimethylformamide were added, and heated and stirred at 80°C under a nitrogen atmosphere for 1.5 hours. After cooling to room temperature, the oil and water were separated using ion-exchanged water. The solvent was removed to obtain a photopolymerization initiator (A7). Photopolymerization initiator (A7) has Chemical Formula 11.

[0086]

[0087] [Photopolymerization initiator (A8)]

[0088] 82 g of diphenyl sulfide, 57 g of methyl chlorooxalyl ester, and 150 mL of dichloromethane were cooled in an ice-water bath at approximately 5°C. Then, 73 g of aluminum trichloride was slowly added portionwise to the reaction system while stirring for two hours. The dichloromethane solution containing the product was poured into ice water with continuous stirring. The dichloromethane layer was washed with deionized water and the dichloromethane product solution was rotary evaporated to yield a pale yellow solid, Compound h1.

[0089] Stir 81.7 g of compound h1, 100 mL of dichloromethane, and 45 g of aluminum trichloride in an ice-water bath at approximately 0°C. Then, slowly add 26 g of thionyl chloride dropwise to the reaction system until the starting material volume remains constant. Next, slowly add 100 mL of ice-cold deionized water dropwise to the reaction system. The aqueous layer is the aqueous solution of compound h2.

[0090] 17 g of KPF6 solid was added to the aqueous solution of compound h2 for ion exchange. Deionized water was then added with stirring. As the KPF6 solid dissolved, the target product, photopolymerization initiator (A8), gradually precipitated. The product was filtered, recrystallized from methanol, and dried to obtain the photopolymerization initiator (A8) as a white solid. Photopolymerization initiator (A8) has the chemical formula 12.

[0091]

[0092] [Preparation of Black Colorant (B)]

[0093] [Black colorant (B1)]

[0094] As the black colorant (B1), carbon black pigment is used.

[0095] [Black colorant (B2)]

[0096] The black colorant (B2) comprises a colorant composition comprising 10 wt% to 40 wt% of CI Pigment Yellow 138, 10 wt% to 40 wt% of CI Pigment Violet 29, 0 wt% to 15 wt% of an oxanthone dye, and 30 wt% to 60 wt% of CI Pigment Blue 15:6. The optical absorption spectrum of the black colorant (B2) exhibits an OD (optical density) of 1 to 1.5 within a wavelength range of 380 nm to 440 nm, an OD of 1.5 or greater within a wavelength range of 440 nm to 540 nm, an OD of 1 to 1.5 within a wavelength range of 540 nm to 720 nm, and an OD of 1 or less within a wavelength range of 720 nm to 780 nm.

[0097] [Black colorant (B3)]

[0098] The black colorant (B3) comprises 10-40 wt% of CI Pigment Orange 64, 10-40 wt% of CI Pigment Violet 29, 0-15 wt% of an oxanthone dye, and 30-60 wt% of CI Pigment Blue 15:6. The optical absorption spectrum of the black colorant (B3) exhibits an OD value of 1-1.5 within a wavelength range of 380-440 nm, an OD value of 1.5 or greater within a wavelength range of 440-530 nm, an OD value of 1-1.5 within a wavelength range of 530-640 nm, and an OD value of 1 or less within a wavelength range of 640-780 nm.

[0099] [Leveling agent]

[0100] As the leveling agent, polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) was used.

[0101] [Solvent]

[0102] Propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent.

[0103] [Property Analysis]

[0104] [Spectrum overlap area]

[0105] The photopolymerization initiator spectrum is obtained by dissolving the photopolymerization initiator (A) in propylene glycol monomethyl ether acetate at a ratio of 1:9. The mixture is then placed in a UV-Vis spectrometer (Lambda 850) and the optical absorption spectrum is measured from 200nm to 600nm. The measured data is normalized based on the maximum optical absorption intensity (i.e., the normalized value is 1), and the normalized data is plotted as the photopolymerization initiator spectrum (optical absorption spectrum).

[0106] The exposure spectrum diagram is obtained by measuring the exposure optical spectrum of a mercury lamp exposure machine using an optical spectrometer (Ocean Optic USB 2000+). The measured data is normalized at the maximum exposure intensity, and the normalized data is plotted as the exposure spectrum diagram (exposure optical spectrum diagram).

[0107] Please refer to Figure 1 , stack the spectrum of the photopolymerization initiator and the spectrum of the exposure machine, and calculate the overlapping area between the two spectra in the wavelength range of 350nm to 380nm of the i-Line light source used by the mercury lamp exposure machine, that is, the area of ​​the solid line area, in nm*%. It can be understood that Figure 1The units on the vertical axis can be considered as arbitrary units (au), and the areas of the solid lines can be considered as unitless.

[0108] [Reliability Analysis]

[0109] The reliability assessment method involves coating a black photosensitive resin composition to a thickness of 1 to 4 μm. The composition is then left to stand, exposed and developed, and baked at 200°C to 250°C for 20 to 25 minutes to produce a black film (which can be used as a black optical element). The black film is then used as a test piece to test its heat resistance, chemical resistance, and UV resistance.

[0110] The heat resistance test method involves measuring the optical density (OD) of the pre-baking black film test piece. The test piece is then placed in a 200°C to 250°C environment for 60 to 180 minutes, and the post-baking OD value is measured. The OD value before baking is subtracted from the post-baking OD value to obtain the delta OD.

[0111] The chemical resistance test method is to first measure the OD value of the newly obtained (black film) test piece before immersion. Then, soak the test piece in an N-methylpyrrolidone solution at a temperature of 15°C to 80°C for 5 to 30 minutes, and then measure the OD value after immersion. Subtract the OD value before immersion from the OD value after immersion to obtain the ΔOD value.

[0112] The UV resistance test method is to first measure the OD value of the newly obtained (black film) test piece before exposure. Then, after irradiating the test piece with UV light for 10 to 60 minutes, measure the OD value after exposure. Subtract the OD value before exposure from the OD value after exposure to obtain the delta OD value.

[0113] The black film test piece's heat resistance, chemical resistance, and UV resistance were evaluated by adding the total ΔOD values. A total ΔOD ≤ 0.3 was considered acceptable. The results are shown in Tables 1 and 2.

[0114] The peeling test was performed by visually observing the developed (black film) test piece to see if there was any peeling. The results are shown in Tables 1 and 2. The symbol ○ indicates no peeling. The symbol △ indicates less than 50% peeling. The symbol X indicates more than 50% peeling.

[0115] Table 1

[0116]

[0117]

[0118] Table 2

[0119]

[0120] It can be seen from Table 1 and Table 2 that the optical elements formed from the colored photosensitive resin compositions of the examples all have good reliability quality.

[0121] Experimental results show that changing the type of resin in the colored photosensitive resin composition does not substantially affect the total ΔOD results. Tables 3 and 4 list the weight percentages of resin (C1), resin (C2), and resin (C3) used in the black photosensitive resin compositions of Examples and Comparative Examples, along with the total ΔOD results. The black photosensitive resin compositions in Tables 1 and 2 consist solely of resin (C1), corresponding to the data in Tables 3 and 4 where resin (C1) is 100 wt%. Tables 3 and 4 also show the ΔOD results when different types / compositions of resins are used in the black photosensitive resin compositions of Tables 1 and 2.

[0122] Table 3

[0123]

[0124]

[0125] Table 4

[0126]

[0127]

[0128] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A colored photosensitive resin composition, characterized in that: Include: A photopolymerization initiator, wherein an optical absorption spectrum of the photopolymerization initiator in the wavelength range of 350 nm to 380 nm and an exposure optical spectrum of a mercury lamp exposure machine have an overlapping area of ​​636.7 to 675; Black colorant; Resin; Photopolymerizable monomers; as well as solvents; The photopolymerization initiator has the chemical formula 2. The colored photosensitive resin composition according to claim 1, wherein The colored photosensitive resin composition is a black photosensitive resin composition.

3. The colored photosensitive resin composition according to claim 1, wherein The black colorant is selected from the group consisting of the following materials: a black pigment; a black dye; a black colorant consisting of 10wt% to 40wt% of CI Pigment Yellow 138, 10wt% to 40wt% of CI Pigment Violet 29, 0wt% to 15wt% of an oxanthone dye, and 30wt% to 60wt% of CI Pigment Blue 15:6; and a black colorant consisting of 10wt% to 40wt% of CI Pigment Orange 64, 10wt% to 40wt% of CI Pigment Violet 29, 0wt% to 15wt% of an oxanthone dye, and 30wt% to 60wt% of CI Pigment Blue 15:

6.

4. The colored photosensitive resin composition according to claim 1, wherein The photopolymerization initiator accounts for 1 wt % to 10 wt % of the colored photosensitive resin composition.

5. The colored photosensitive resin composition according to claim 1, wherein The black colorant accounts for 1 wt % to 30 wt % of the colored photosensitive resin composition.

6. The colored photosensitive resin composition according to claim 1, wherein The resin accounts for 20 wt % to 80 wt % of the colored photosensitive resin composition.

7. The colored photosensitive resin composition according to claim 1, wherein The photopolymerizable monomer accounts for 10 wt % to 40 wt % of the colored photosensitive resin composition.

8. The colored photosensitive resin composition according to claim 1, wherein The solvent accounts for 1 wt % to 50 wt % of the colored photosensitive resin composition. 9 . An optical element formed from the colored photosensitive resin composition according to claim 1 .

10. A display device comprising the optical element according to claim 9.

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