Black resin composition, hardened film, and black filter

Abstract

The present invention provides a black resin composition, a hardened film, and a black filter. The black resin composition includes a black colorant (A), an ethylenically unsaturated monomer (B), a solvent (C), a resin (D), a photoinitiator (E), a UV absorber (F), and a surfactant (G), wherein the resin (D) includes a first resin having a weight average molecular weight of 2,000 to 20,000, the first resin includes a structural unit having a fluorene ring and two or more ethylenically polymerizable groups, and the UV absorber (F) includes a benzylidene derivative.

Description

Technical Field

[0001] This invention relates to a resin composition, a hardened film, and a filter, and particularly to a black resin composition, a hardened film, and a black filter. Background Technology

[0002] The light emitted by a liquid crystal display (LCD) device exhibits a certain frequency and periodicity over time, and also varies with different brightness and color levels. If the light source is not driven by suitable electronic circuitry (such as a ballast, driver, or power supply), the emitted light will flicker (i.e., screen flicker), and the greater the fluctuation in output luminous flux, the more severe the flicker. The operating current of the light source inevitably fluctuates with the input voltage, directly causing fluctuations in light output and resulting in flicker. Especially when the light source operates at high brightness, flicker becomes more severe, potentially causing the Complementary Metal-Oxide Semiconductor (CMOS) image sensor to malfunction.

[0003] Generally, black filters are used in liquid crystal display devices to reduce the amount of light transmitted in the visible light region, thereby controlling the saturation time of the CMOS image sensing element and improving flicker. However, the resin compositions currently used and the black filters made from them cannot simultaneously achieve good resolution, developability, and adhesion. Summary of the Invention

[0004] In view of this, the present invention provides a black resin composition, a hardened film, and a black filter that simultaneously possess good resolution, developability, and adhesion, and also have appropriate light transmittance at a certain thickness.

[0005] The present invention provides a black resin composition comprising: a black colorant (A), an ethylene unsaturated monomer (B), a solvent (C), a resin (D), a photoinitiator (E), an ultraviolet absorber (F), and a surfactant (G), wherein the resin (D) comprises a first resin having a weight average molecular weight of 2,000 to 20,000, the first resin comprising a structural unit having a fluorene ring and two or more ethylene polymerizable groups, and the ultraviolet absorber (F) comprises a benzylidene derivative.

[0006] According to an embodiment of the present invention, the above-mentioned structural unit having a fluorene ring and two or more ethylene polymerizable groups is the structural unit shown in the following formula (1):

[0007]

[0008] In equation (1), * indicates the bond position.

[0009] According to an embodiment of the present invention, the black colorant (A) described above includes carbon black (A-1) and titanium black (A-2), wherein the particle size of the carbon black (A-1) and the titanium black (A-2) is less than 80 nm.

[0010] According to an embodiment of the present invention, the above-mentioned ethylene unsaturated monomer (B) is a monomer having four or more (meth)acryloyl groups.

[0011] According to an embodiment of the present invention, the solvent (C) described above includes a propylene glycol ether solvent (C-1), wherein the propylene glycol ether solvent (C-1) is selected from at least one of the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, and propylene glycol monopropyl ether.

[0012] According to an embodiment of the present invention, the above-mentioned photoinitiator (E) includes an oxime ester-based photoinitiator.

[0013] According to an embodiment of the present invention, the vinyl unsaturated monomer (B) is 100 parts by weight, and the oxime ester photoinitiator is 1 to 50 parts by weight.

[0014] According to an embodiment of the present invention, the vinyl unsaturated monomer (B) is 100 parts by weight, and the benzylidene derivative is 1.28 to 2.35 parts by weight.

[0015] According to embodiments of the present invention, the surfactant (G) described above includes at least one selected from the group consisting of fluorinated surfactants (G-1), siloxane surfactants (G-2), and nonionic surfactants (G-3).

[0016] The present invention provides a hardened film formed from the above-mentioned black resin composition, wherein the hardened film has a visible light transmittance of 5% to 50% when the thickness is 0.2 μm.

[0017] The present invention provides a black filter formed from the above-mentioned black resin composition, wherein the visible light transmittance of the black filter is 5% to 50% when the thickness is 0.2 μm.

[0018] Based on the above, the black resin composition of the present invention includes a specific resin and a specific ultraviolet absorber. Therefore, when the black resin composition is used to form a hardened film or a black filter, the hardened film or black filter can have good resolution, developability, and adhesion, and also has appropriate light transmittance at a certain thickness, thereby improving the phenomena of excessive developing residue, pattern edge defects, and poor adhesion. Attached Figure Description

[0019] none Detailed Implementation

[0020] <Black Resin Composition>

[0021] This embodiment provides a black resin composition comprising a black colorant (A), an ethylene unsaturated monomer (B), a solvent (C), a resin (D), a photoinitiator (E), an ultraviolet absorber (F), and a surfactant (G). Furthermore, if desired, the black resin composition may also include other additives (H). The various components used in the black resin composition will be described in detail below.

[0022] It is worth mentioning that the hardened film or black filter formed by the black resin composition in this embodiment has a visible light transmittance of 5% to 50% when the thickness is 0.2 μm. Therefore, when applied to display devices, it can effectively reduce the amount of light transmitted in the visible light region, thereby controlling the saturation time of the CMOS image sensing component and improving the flicker phenomenon.

[0023] In this specification, "visible light transmittance" refers to the transmittance at wavelengths of 380 nm to 780 nm.

[0024] In this specification, "(meth)acrylic acid" means "acrylic acid" and / or "methacrylic acid"; "(meth)acrylate" means "acrylate" and / or "methacrylate"; "(meth)acryloyl" means "acryloyl" and / or "methacryloyl"; and "(meth)acrylamide" means "acrylamide" and / or "methacrylamide".

[0025] Black colorant (A)

[0026] The black colorant (A) includes titanium black (A-1) and carbon black (A-2). However, this embodiment is not limited to this; the black colorant (A) may also include organic black pigments (e.g., lactam-based organic black, RGB black, RVB black, etc.), inorganic black pigments (e.g., aniline black, perylene black, anthocyanin black, lignin black, etc.), combinations of the aforementioned black pigments, or other suitable black colorants.

[0027] There are no particular restrictions on the particle size of titanium black (A-1) and carbon black (A-2). Appropriate particle sizes can be selected according to requirements, preferably less than 80 nanometers (nm). When the particle size of titanium black (A-1) and carbon black (A-2) is less than 80 nm, the hardened film and black filter formed by the black resin composition can have better resolution.

[0028] Based on 100 parts by weight of ethylene unsaturated monomer (B) and 500 to 1500 parts by weight of black colorant (A), preferably 500 to 900 parts by weight.

[0029] Ethylene unsaturated monomer (B)

[0030] The vinyl unsaturated monomer (B) may be a monomer having four or more (meth)acryloyl groups, preferably a monomer having six or more (meth)acryloyl groups. When the vinyl unsaturated monomer (B) is a monomer having four or more (meth)acryloyl groups, the hardened film and black filter formed by the black resin composition can have better resolution and adhesion.

[0031] Specifically, examples of vinyl unsaturated monomers (B) may include dipentaerythritol hexaacrylate (DPHA), polyfunctional polyurethane acrylate (trade name DPHA-40H, manufactured by Nippon Kayaku Co., LTD), ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. Pentaerythritol pentaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether Di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glyceryl triacrylate, glyceryl polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate, reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, N,N'-methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyols with N-hydroxymethyl (meth)acrylate The condensate of acrylamide, triacrylate methyl acetal, 9,9-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-chloro-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, biscresol fluorene dimethacrylate, or combinations thereof. Specific examples of the vinyl unsaturated monomer (B) preferably include dipentaerythritol hexaacrylate and polyfunctional polyurethane acrylate (trade name: DPHA-40H, manufactured by Nippon Kayaku Co., LTD), or combinations thereof. The vinyl unsaturated monomer (B) can be used alone or in combination with multiple monomers.

[0032] Solvent (C)

[0033] There are no particular restrictions on the solvent (C), and an appropriate solvent can be selected according to the requirements. Specifically, solvent (C) includes propylene glycol ether solvents (C-1). In addition, solvent (C) may also include ethylene glycol ether solvents (C-2).

[0034] The propylene glycol ether solvent (C-1) is selected from at least one of the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether and propylene glycol monopropyl ether.

[0035] Specific examples of glycol ether solvents (C-2) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, or combinations thereof.

[0036] Solvent (C) can be used alone or in combination.

[0037] Based on the following: 100 parts by weight of vinyl unsaturated monomer (B) and 500 to 1500 parts by weight of propylene glycol ether solvent (C-1), preferably 600 to 1200 parts by weight, and even more preferably 700 to 1160 parts by weight.

[0038] Based on the ethylene unsaturated monomer (B) being 100 parts by weight and the solvent (C) being 500 to 1500 parts by weight, preferably 800 to 1400 parts by weight.

[0039] Resin (D)

[0040] Resin (D) includes a first resin. The first resin includes structural units having a fluorene ring and two or more vinyl polymerizable groups. The weight average molecular weight of the first resin is 2,000 to 20,000, preferably 3,000 to 7,000, and more preferably 4,500 to 5,000.

[0041] Specifically, the structural unit having a fluorene ring and two or more vinyl polymerizable groups is preferably the structural unit shown in the following formula (1):

[0042]

[0043] In equation (1), * indicates the bond position.

[0044] Furthermore, a preferred example of the structural unit shown in equation (1) includes a single unit represented by the following equation (1-1).

[0045]

[0046] The first resin is a cardo resin formed by polymerizing a monomer having a fluorene ring and two or more vinyl polymerizable groups, a tetracarboxylic acid dianhydride, and a dicarboxylic acid. There are no particular restrictions on the tetracarboxylic acid dianhydride and the dicarboxylic acid; appropriate tetracarboxylic acid dianhydride and dicarboxylic acid can be selected according to requirements.

[0047] Furthermore, there are no particular restrictions on the method for synthesizing the first resin. Conventional organic synthesis methods can be used to polymerize monomers having a fluorene ring and two or more vinyl polymerizable groups, tetracarboxylic acid dianhydrides, and dicarboxylic acids into structural units having a fluorene ring and two or more vinyl polymerizable groups.

[0048] Specific examples of the first resin include Cardo resin (trade name KBR series, KISCO Ltd.).

[0049] Based on 100 parts by weight of ethylene unsaturated monomer (B), the first resin is 50 to 300 parts by weight, preferably 100 to 250 parts by weight.

[0050] When the black resin composition includes the first resin, the hardened film and black filter formed by the black resin composition can have good resolution and developability. Conversely, when the black resin composition does not include the first resin, the hardened film and black filter formed by the black resin composition have poor resolution and developability. Furthermore, when the content of the first resin included in the black resin composition is within the above-mentioned range, the hardened film and black filter formed by the black resin composition can have better resolution and developability.

[0051] Furthermore, when the content of the oxime ester photoinitiator contained in the black resin composition falls within the above range, the hardened film and black filter formed by the black resin composition can have better resolution.

[0052] Furthermore, this embodiment is not limited to this; the resin (D) may also include other resins besides the first resin.

[0053] Photoinitiator (E)

[0054] The photoinitiator (E) may include oxime ester-based photoinitiators. However, this embodiment is not limited to this; the photoinitiator (E) may also include other suitable photoinitiators.

[0055] There are no particular limitations on oxime ester-based photoinitiators; appropriate oxime ester-based photoinitiators can be selected according to requirements. Specifically, examples of oxime ester-based photoinitiators include Photocure 4456 (manufactured by Eutec), Irgacure OXE-01, OXE-02, OXE-03, OXE-04 (trade name; manufactured by BASF), or other suitable oxime ester-based photoinitiators. Oxime ester-based photoinitiators can be used alone or in combination.

[0056] Based on the ethylene unsaturated monomer (B) being 100 parts by weight, and the oxime ester photoinitiator being 1 to 50 parts by weight, preferably 5 to 15 parts by weight.

[0057] When the photoinitiator (E) in the black resin composition includes an oxime ester-based photoinitiator, the hardened film and black filter formed by the black resin composition can have better resolution. Furthermore, when the content of the oxime ester-based photoinitiator in the black resin composition falls within the above-mentioned range, the hardened film and black filter formed by the black resin composition can have even better resolution.

[0058] Ultraviolet absorber (F)

[0059] Ultraviolet absorbers (F) include benzylidene derivatives.

[0060] Specifically, benzylidene derivatives are compounds having a benzylidene group as shown in formula (2).

[0061]

[0062] In equation (2), * indicates the location of the bond.

[0063] Specific examples of benzylidene derivatives include 4-methylbenzylidene camphor, 1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptane-2-one, benzylidene camphor sulfonic acid, polyacrylamide methylbenzylidene camphor, dimethyl malonate (4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonate, and dibenzylidene rings. Pentanone, di(p-methoxybenzyl)cyclopentanone, di(p-nitrobenzyl)cyclopentanone, di(m-nitrobenzyl)cyclopentanone, di(p-chlorobenzyl)cyclopentanone, dibenzylcyclohexanone, di(p-methoxybenzyl)cyclohexanone, di(p-nitrobenzyl)cyclohexanone, di(m-nitrobenzyl)cyclohexanone, di(p-chlorobenzyl)cyclohexanone, 2,4,6-tris(diisobutyl-4′-aminobenzylmalonate)-me-tri Ultraviolet absorber (UV1990, manufactured by Eutec, maximum absorption wavelength: 384 nm), or other suitable benzylidene derivatives. A single benzylidene derivative may be used, or multiple derivatives may be used in combination.

[0064] Based on the fact that the vinyl unsaturated monomer (B) is 100 parts by weight and the benzylidene derivative is 1.28 to 2.35 parts by weight.

[0065] When the ultraviolet absorber (F) in the black resin composition includes a benzylidene derivative, the hardened film and black filter formed by the black resin composition can have good resolution. However, when the black resin composition does not contain a benzylidene derivative, the adhesion of the hardened film and black filter formed by the black resin composition is insufficient, making it impossible to simultaneously achieve good resolution, developability, and adhesion. Furthermore, when the benzylidene derivative contained in the black resin composition falls within the above-mentioned range, the hardened film and black filter formed by the black resin composition can have good resolution without the formation of excessively small patterns.

[0066] It is worth mentioning that the black resin composition of this embodiment is combined with a first resin having a structural unit having a fluorene ring and two or more ethylene polymerizable groups and an ultraviolet absorber (F) including a benzylidene derivative, thereby providing a black resin composition, a hardened film and a black filter that simultaneously have good resolution, developability and adhesion.

[0067] Surfactant (G)

[0068] Surfactants (G) include at least one of the group consisting of fluorinated surfactants (G-1), siloxane surfactants (G-2), and nonionic surfactants (G-3).

[0069] Specific examples of fluorinated surfactants (G-1) include Megaface F444, F477, F554, F556, F563, F575, RS-72-K (trade name; manufactured by DIC Inc.) or other suitable fluorinated surfactants. Fluorinated surfactants can be used alone or in combination.

[0070] Specific examples of siloxane surfactants (G-2) include polysiloxane surfactants. Specifically, siloxane surfactants may include BYK-307, BYK-323, BYK-348 (trade name; manufactured by BYK Chemical Co., Ltd.), KP323, KP324, KP340, KP341 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) or other suitable siloxane surfactants. Siloxane surfactants may be used alone or in combination.

[0071] Specific examples of nonionic surfactants (G-3) include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters.

[0072] Based on the ethylene unsaturated monomer (B) being 100 parts by weight and the surfactant (G) being 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight.

[0073] When the black resin composition includes a surfactant (G), the hardened film and black filter formed by the black resin composition can have good coating uniformity. When the content of surfactant (G) included in the black resin composition falls within the above range, the hardened film and black filter formed by the black resin composition have even better coating uniformity.

[0074] Additive (H)

[0075] Without affecting the efficacy of the present invention, the black resin composition may be selectively further supplemented with additives (H). There are no particular limitations on additives (H), but specifically, additives (H) may include stabilizers, antioxidants, etc.

[0076] <Preparation Method of Black Resin Composition>

[0077] There are no particular limitations on the preparation method of the black resin composition; an appropriate method for mixing various components can be selected according to requirements. For example, a black colorant (A), an ethylene unsaturated monomer (B), a solvent (C), a resin (D), a photoinitiator (E), an ultraviolet absorber (F), and a surfactant (G) can be placed in a stirrer and stirred until they are uniformly mixed into a solution. If necessary, an additive (H) can also be added. After mixing them evenly, a liquid black resin composition can be obtained.

[0078] Hardened membrane

[0079] The hardened film is formed from the aforementioned black resin composition. In one embodiment, the hardened film has a visible light transmittance of 5% to 50% at a thickness of 0.2 μm, making it suitable for use with black filters and giving the black filters a specific light transmittance.

[0080] The hardened film can be formed by coating the above-mentioned resin composition onto a substrate to form a coating film, and then subjecting the coating film to pre-bake, exposure, development, and post-bake. Specifically, after coating the black resin composition onto the substrate to form a coating film, it is pre-baked at a temperature of 90°C for 2 minutes. Then, the pre-baked coating film is exposed at 1400 J / m using an i-line exposure machine (wavelength 365 nm). 2 Then, it is developed with developer at 23°C for 84 seconds. Next, it is baked at 220°C for 5 minutes to form a hardened film on the substrate.

[0081] The substrate can be a glass substrate, a silicon wafer substrate, or a plastic substrate material (such as a polyethersulfone (PES) board or a polycarbonate (PC) board), and there are no particular restrictions on its type.

[0082] There are no particular restrictions on the coating method, but spraying, roller coating, spin coating, or similar methods can be used, and spin coating is generally widely used. Furthermore, a coating film is formed, and in some cases, residual solvent can be partially removed under reduced pressure.

[0083] There are no particular restrictions on the developer; an appropriate developer can be selected based on the requirements. Specifically, the developer can be tetramethyl ammonium hydroxide (TMAH) at a concentration of 0.3% by weight.

[0084] <Black Filter>

[0085] An exemplary embodiment of the present invention provides a black filter, which is the aforementioned hardened film. Furthermore, the manufacturing method of the black filter can be the same as the manufacturing method of the aforementioned hardened film, and will not be described again here.

[0086] The hardened film or black filter film provided in the exemplary embodiments of the present invention has a specific transmittance in the visible light region and can be applied to CMOS image sensors (CIS), solid-state imaging components, integrated circuit (IC) semiconductors, light-emitting diodes, liquid crystal displays, etc.

[0087] Examples of black resin compositions and cured films

[0088] Examples 1 to 5 and Comparative Examples 1 to 2 of the black resin composition and the hardened film are described below:

[0089] Example 1

[0090] a. Resin composition

[0091] 279 parts by weight of carbon black with a particle size less than 80 nm, 519 parts by weight of titanium black with a particle size less than 80 nm, 50 parts by weight of dipentaerythritol hexaacrylate, 50 parts by weight of DPHA-40H, 208 parts by weight of calorie resin (molecular weight 5300; manufactured by Gisco Corporation), 12.9 parts by weight of oxime ester photoinitiator (manufactured by Yudi), 1.88 parts by weight of ultraviolet absorber (UV1990, manufactured by Yudi, maximum absorption wavelength: 384 nm), and 2.3 parts by weight of methyl methacrylate fluorinated surfactant were added to a mixed solvent of propylene glycol ethers and ethylene glycol ethers, and stirred evenly with a stirrer to obtain the black resin composition of Example 1.

[0092] b. Hardened membrane

[0093] The black resin compositions prepared in the examples were coated onto the substrate using a spin coater (model TEL-MK8, manufactured by Tokyo Powertech Co., Ltd., with a rotation speed of approximately 1800 rpm). Next, a pre-baking process was performed at 90°C for 2 minutes. Then, exposure was performed at 1400 J / m using an i-line lithography machine (wavelength 365 nm) (model FPA-5500iZa, manufactured by Canon Co., Ltd.). 2 To form a semi-finished product, development was then carried out at 23°C for 84 seconds using 0.3% by weight TMAH as the developer. Afterward, a post-bake at 220°C for 5 minutes yielded the hardened film. The obtained hardened film was evaluated using the following methods, and the results are shown in Table 1.

[0094] Examples 2 to 5 and Comparative Examples 1 to 2

[0095] The resin compositions of Examples 2 to 5 and Comparative Examples 1 to 2 were prepared using the same steps as in Example 1, except that the types and amounts of the components in the black resin composition were changed (as shown in Table 1). The obtained black resin compositions were formed into hardened films and evaluated using the following evaluation methods, and the results are shown in Table 1.

[0096]

[0097] The trade names of the ingredients / compounds listed in Table 1 are shown in Table 2 below.

[0098] [Table 2]

[0099]

[0100] <Evaluation Method>

[0101] a. Resolution

[0102] The prepared hardened film (0.2 μm thick) was examined at 45K magnification using a critical dimension scanning electron microscope (CD-SEM) (model: S-8840, manufactured by Hitachi) to evaluate the integrity of the dot pattern in a region with a critical dimension of 1.0 μm. A more complete pattern outline indicates better resolution of the hardened film.

[0103] The evaluation criteria for resolution are as follows:

[0104] ○: The pattern outline is complete;

[0105] △: The pattern outline may protrude slightly or have missing corners, but this does not affect its practical application;

[0106] ×: The pattern outline is incomplete.

[0107] b. Radioactivity

[0108] The prepared hardened film (0.2 μm thick) was examined at 35 K magnification using a critical dimension scanning electron microscope (CD-SEM) (model: S-8840, manufactured by Hitachi) to observe the unexposed area of ​​the critical dimension 1 μm region for residue, in order to evaluate its developability. Less residue indicates better developability of the hardened film.

[0109] The evaluation criteria for radioactivity are as follows:

[0110] ○: No residue;

[0111] △: Slight residue may remain, but it does not affect practical application;

[0112] ×: There are obvious residues.

[0113] c. Adhesion

[0114] The prepared hardened film (0.2 μm thick) was observed at 50x magnification using an optical microscope (OM, model: BH3-SIC6, manufactured by Olympus) to evaluate the adhesion by measuring the minimum width of the pattern that prevents it from peeling off. A smaller width at which the pattern does not peel off indicates better adhesion of the hardened film.

[0115] The evaluation criteria for adhesion are as follows:

[0116] ○: 1μm ≤ pattern width < 2μm;

[0117] △: 2μm ≤ pattern width < 3μm;

[0118] ×: 3μm ≤ pattern width.

[0119] d. Light transmittance

[0120] The transmittance of the prepared hardened film (thickness of 0.2 μm) was measured at 13 selected points on the film using a colorimeter (model: MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) at wavelengths ranging from 380 nm to 780 nm. The average transmittance obtained was taken as the light transmittance shown in Table 1.

[0121] <Evaluation Results>

[0122] As shown in Table 1, when the black resin composition contains both calorie resin and benzylidene ultraviolet absorber (Examples 1-5), the hardened film formed by the black resin composition has good resolution, developability and adhesion, and can be used for black filters.

[0123] In contrast, when the black resin composition does not contain calorie resin (Comparative Example 1), the hardened film formed by the black resin composition has poor resolution and developability; when the black resin composition does not contain benzylidene ultraviolet absorber (Comparative Example 2), the hardened film formed by the black resin composition has insufficient adhesion, and thus cannot simultaneously possess good resolution, developability, and adhesion.

[0124] In summary, when the black resin composition of the present invention contains both calorie resin as a resin and benzylidene derivative as an ultraviolet absorber, the hardened film or black filter formed from the black resin composition simultaneously possesses good resolution, developability, and adhesion, and also has appropriate light transmittance at a certain thickness. Therefore, it can be applied to hardened films or black filters, thereby improving the performance of using hardened films or black filters.

[0125] 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 resin composition, characterized in that, include: Black colorant (A); Ethylene unsaturated monomer (B); Solvent (C); Resin (D); Photoinitiator (E); Ultraviolet absorber (F); and Surfactant (G) The resin (D) comprises a first resin with a weight average molecular weight of 2,000 to 20,000, the first resin comprising a structural unit having a fluorene ring and two or more vinyl polymerizable groups, the structural unit having a fluorene ring and two or more vinyl polymerizable groups being the structural unit shown in the following formula (1). The ultraviolet absorber (F) includes benzylidene derivatives: Equation (1) In equation (1), * indicates the bond position. The benzylidene derivatives are selected from 4-methylbenzylidene camphor, 1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptane-2-one, benzylidene camphor sulfonic acid, polyacrylamide methylbenzylidene camphor, dimethyl malonate (4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonate, dibenzylidene cyclopentanone, and di(p-methoxybenzylidene) Cyclopentanone, di(p-nitrobenzylidene)cyclopentanone, di(m-nitrobenzylidene)cyclopentanone, di(p-chlorobenzylidene)cyclopentanone, dibenzylidene cyclohexanone, di(p-methoxybenzylidene)cyclohexanone, di(p-nitrobenzylidene)cyclohexanone, di(m-nitrobenzylidene)cyclohexanone, di(p-chlorobenzylidene)cyclohexanone, 2,4,6-tris(diisobutyl-4'-aminobenzylidene malonate)-tris(diisobutyl-4'-aminobenzylidene malonate), and ultraviolet absorbers of the model name UV1990 manufactured by Ubisoft with a maximum absorption wavelength of 384 nm, or combinations thereof.

2. The black resin composition according to claim 1, wherein the black colorant (A) comprises carbon black (A-1) and titanium black (A-2), wherein the particle size of the carbon black (A-1) and the titanium black (A-2) is less than 80 nm.

3. The black resin composition according to claim 1, wherein the vinyl unsaturated monomer (B) is a monomer having four or more (meth)acryloyl groups.

4. The black resin composition according to claim 1, wherein the solvent (C) comprises a propylene glycol ether solvent (C-1), wherein the propylene glycol ether solvent (C-1) is selected from at least one of the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, and propylene glycol monopropyl ether.

5. The black resin composition according to claim 1, wherein the photoinitiator (E) comprises an oxime ester-based photoinitiator.

6. The black resin composition according to claim 5, wherein the vinyl unsaturated monomer (B) is 100 parts by weight and the oxime ester photoinitiator is 1 to 50 parts by weight.

7. The black resin composition according to claim 1, wherein the vinyl unsaturated monomer (B) is 100 parts by weight and the benzylidene derivative is 1.28 to 2.35 parts by weight.

8. The black resin composition according to claim 1, wherein the surfactant (G) comprises at least one selected from the group consisting of fluorinated surfactants (G-1), siloxane surfactants (G-2), and nonionic surfactants (G-3).

9. A hardened film, characterized in that, It is formed from the black resin composition according to any one of claims 1 to 8, wherein the hardened film has a visible light transmittance of 5% to 50% when the thickness is 0.2 μm.

10. A black filter, characterized in that, It is formed from the black resin composition according to any one of claims 1 to 8, wherein the black filter has a visible light transmittance of 5% to 50% at a thickness of 0.2 μm.

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