Photosensitive resin composition, photosensitive resin film and color filter produced using the same, and CMOS image sensor

Abstract

To provide a photosensitive resin composition that allows for the coating of the substrate or the lower photosensitive resin layer with a uniform thickness.SOLUTION: The present invention relates to a photosensitive resin composition, and a photosensitive resin layer and a color filter fabricated using the same. According to an embodiment, a photosensitive resin composition includes: (A) an additive; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; (E) a colorant; and (F) a solvent, wherein the additive includes a leveling agent, and the leveling agent constitutes about 15 to 30 ppm of the total amount of the photosensitive resin composition.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film and a color filter produced using the same, and a CMOS image sensor. [Background technology]

[0002] An image sensor is a semiconductor that can convert photons into electrons so that they can be displayed on a screen or stored in a storage device.

[0003] Image sensors are classified into charge coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors according to their manufacturing process and application.

[0004] A complementary metal-oxide semiconductor image sensor (CMOS image sensor, CIS) is a non-memory semiconductor that converts images captured by a camera into digital signals. It is a collection of pixels that include color filters, photodiodes, amplifiers, etc.

[0005] The color filter includes filter segments of additive primary colors of red, green, and blue. The color filter can be manufactured by coating a photosensitive resin composition containing a colorant on a substrate, exposing the substrate to a desired pattern, developing the substrate, and post-baking the substrate to thermally cure the substrate to form a photosensitive resin film, and then repeating this series of processes.

[0006] However, if thickness distribution occurs during the process of coating the photosensitive resin composition onto a substrate or a previously formed photosensitive resin film (hereinafter referred to as the "lower photosensitive resin film"), the surface of the final color filter may become physically rough. Summary of the Invention [Problem to be solved by the invention]

[0007] One object of one embodiment is to provide a photosensitive resin composition that is coated with a uniform thickness on a substrate or a lower photosensitive resin film.

[0008] Another embodiment has an object to provide a photosensitive resin film produced using the photosensitive resin composition.

[0009] Another object of the present invention is to provide a color filter manufactured using the photosensitive resin film. [Means for solving the problem]

[0010] In one embodiment, the photosensitive resin composition includes (A) an additive, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a colorant, and (F) a solvent, and the additive includes a leveling agent, and the leveling agent is included in an amount of 15 ppm to 30 ppm of the total amount of the photosensitive resin composition.

[0011] The leveling agent may be included in the total composition in an amount of 20 ppm to 25 ppm.

[0012] The leveling agent may be a fluorosurfactant.

[0013] The fluorosurfactant may be a non-ionic fluorosurfactant.

[0014] The additive may further include a dispersion medium.

[0015] The leveling agent may be contained in an amount of 1% to 20% by weight in the total amount of the additives.

[0016] The weight ratio of the leveling agent and the colorant may be from 1:700 to 1:900.

[0017] The additives may further include at least one additive selected from malonic acid, 3-amino-1,2-propanediol, a coupling agent containing a vinyl group or a (meth)acryloxy group, and a radical polymerization initiator.

[0018] The binder resin may include an acrylic binder resin, an epoxy binder resin, or a combination thereof.

[0019] The colorant may include a blue pigment, a violet pigment, or a combination thereof.

[0020] The solvent may include two or more solvents having different boiling points.

[0021] The solvent may include two or more of the following solvents: propylene glycol monomethyl ether acetate (PGMEA), n-butyl alcohol (n-BA), and diethylene glycol methyl ethyl ether (MEDG).

[0022] The photosensitive resin composition may contain, relative to the total amount of the photosensitive resin composition, 15 ppm to 30 ppm of the (A) additive, 1 wt % to 20 wt % of the (B) binder resin, 1 wt % to 20 wt % of the (C) photopolymerizable compound, 0.1 wt % to 5 wt % of the (D) photopolymerization initiator, 5 wt % to 70 wt % of the (E) colorant, and the balance of the (F) solvent.

[0023] The photosensitive resin composition may have a viscosity at 25° C. of 1.5 cP to 3.8 cP.

[0024] In another embodiment, there is provided a photosensitive resin film produced using the photosensitive resin composition.

[0025] In another embodiment, there is provided a color filter including the photosensitive resin film.

[0026] In another embodiment, a CMOS image sensor including the photosensitive color filter is provided.

[0027] Further details of other aspects of the invention are included in the detailed description below. Effect of the Invention

[0028] In one embodiment, the photosensitive resin composition contains a leveling agent in a specific content range, so that the photosensitive resin composition can be coated with a uniform thickness on a substrate or a lower photosensitive resin film.

[0029] As a result, the photosensitive resin film and color filter manufactured using the photosensitive resin composition of one embodiment have excellent surface smoothness, which can contribute to realizing a certain level of image quality of the image sensor. [Brief description of the drawings]

[0030] [Figure 1] 10 is a schematic diagram showing an exposure pattern according to an evaluation example. [Diagram 2] 1 shows a thickness profile according to an evaluation example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] Hereinafter, the present invention will be described in detail with reference to the examples. However, the following description is given for illustrative purposes only and does not limit the present invention, and the present invention is defined by the claims.

[0032] In this specification, unless otherwise specified, "substituted" means that at least one hydrogen atom in a compound is substituted with a substituent selected from the group consisting of a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

[0033] In this specification, unless otherwise specified, the terms "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" refer to cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene groups each having at least one N, O, S or P heteroatom in the ring compound.

[0034] In this specification, unless otherwise specified, "(meth)acrylate" includes both "acrylate" and "methacrylate".

[0035] In the chemical formulas herein, unless otherwise defined, when a chemical bond is not drawn at a position where a chemical bond should be drawn, this means that a hydrogen atom is bonded at that position.

[0036] In this specification, unless otherwise defined, "*" means a moiety connected to the same or different atom or chemical formula.

[0037] In this specification, "particle size" or "particle diameter" is defined as the size of a particle based on the particle size distribution. Specifically, the particle size or particle diameter "Dn" refers to the particle size when particles distributed in various particle sizes are accumulated to "n%" by volume. For example, D50 refers to the particle size when particles are accumulated to 50% by volume.

[0038] The size of the particles or the particle size "Dn" can be measured by methods well known to those skilled in the art, for example, by a particle size analyzer, or by transmission electron microscopy or scanning electron microscopy. Alternatively, it can be measured by performing data analysis on the results obtained using dynamic light scattering.

[0039] (Photosensitive resin composition) One embodiment is a photosensitive resin composition comprising (A) an additive, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a colorant, and (F) a solvent, wherein the additive comprises a leveling agent, and the leveling agent is contained in an amount of 15 ppm to 30 ppm of the total amount of the photosensitive resin composition.

[0040] (A) Additives As previously mentioned, the additives include leveling agents.

[0041] Here, the "leveling agent" refers to an additive that improves the fluidity of the photosensitive resin composition by adjusting the evaporation rate of the solvent or inhibiting the aggregation of the colorant.

[0042] As mentioned above, if a coating thickness distribution occurs during the process of coating a photosensitive resin composition onto a substrate or a lower photosensitive resin film, the surface may become physically rough during the subsequent pattern formation (exposure and development) process.

[0043] In particular, when a photosensitive resin composition is coated on a lower photosensitive resin film, depending on the content of a leveling agent in the photosensitive resin composition, a severe barrier may be induced at the partition, resulting in deviation in the coating thickness. Furthermore, when spin coating is used as the coating method, the coating thickness is likely to be non-uniform at the edge of the substrate or the lower photosensitive resin film compared to the center due to its methodological limitations.

[0044] Exposure to light with such deviations in coating thickness will only result in a deteriorated pattern and a color filter with poor surface smoothness.

[0045] In general, it is known that adding a leveling agent to a photosensitive resin composition helps to uniformly coat the composition on a substrate or an underlying photosensitive resin film. However, the coating uniformity may vary depending on the content of the leveling agent in the photosensitive resin composition.

[0046] In one embodiment, a leveling agent is used, and the content thereof is optimized to allow the photosensitive resin composition to be uniformly coated on the substrate or the lower photosensitive resin film. As a result, the photosensitive resin film and color filter manufactured using the photosensitive resin composition of one embodiment have excellent surface smoothness, and the image quality of the image sensor can be achieved at a certain level.

[0047] In one embodiment, the leveling agent defines only the solid state material, which may be included in the total amount of the photosensitive resin composition at 15 ppm to 30 ppm.

[0048] Within the above range, if the content of the leveling agent is below the lower limit, the effect of the leveling agent is small, whereas if the content of the leveling agent is above the upper limit, the flatness may be deteriorated.

[0049] Within the above range, the higher the content of the leveling agent, the more uniformly the photosensitive resin composition can be coated. For example, the leveling agent may be included in the total amount of the photosensitive resin composition in a range of 15 ppm to 30 ppm, 15 ppm to 25 ppm, or 20 ppm to 25 ppm.

[0050] The leveling agent may be a fluorosurfactant.

[0051] The fluorosurfactant may be produced by subjecting the end of a hydrophobic linear molecule containing a fluorine atom to a substitution reaction with a water-soluble reactor, and can have better surface tension resistance than other surfactants.

[0052] Meanwhile, surfactants can generally be classified into ionic surfactants and nonionic surfactants depending on whether the hydrophilic part is ionic or not, but the fluorosurfactant may be a nonionic fluorosurfactant in which the hydrophilic part is not ionic.

[0053] For example, as the nonionic fluorine-based surfactant, F-554, F-556, F-553, F-559, etc. manufactured by DIC Corporation can be used.

[0054] The additive may further include a dispersion medium in addition to the leveling agent. In this case, the leveling agent may be dispersed in the dispersion medium and used in the form of a leveling agent dilution. The dispersion medium may be selected from the solvents described below.

[0055] The leveling agent in the additive further containing the dispersion medium can be contained in an amount of 1% by weight to 20% by weight. That is, the concentration of the leveling agent in the diluted leveling agent solution may be 1% by weight to 20% by weight.

[0056] Within this range, the leveling agent is uniformly dispersed in the photosensitive resin composition, and thus the surface smoothness of the photosensitive resin film and color filter produced using the photosensitive resin composition can be enhanced.

[0057] For example, the leveling agent in the additive further comprising a dispersing medium can be included in an amount of 1 wt % to 20 wt %, 5 wt % to 15 wt %, or 7 wt % to 12 wt %.

[0058] In one embodiment, the leveling agent as well as the coloring agent define only solid state materials, and the weight ratio of the leveling agent and the coloring agent may be 1:700 to 1:900.

[0059] Within this range, the content of the leveling agent relative to the colorant is appropriately controlled, and the photosensitive resin composition can be uniformly coated on the substrate or the lower photosensitive resin film, provided that within this range, the greater the content of the leveling agent relative to the colorant, the higher the uniformity may be, and the lower the content of the leveling agent relative to the colorant, the lower the uniformity may be.

[0060] Considering such a trade-off relationship, the weight ratio of the leveling agent and the coloring agent can be selected within the range of 1:700 to 1:900, 1:700 to 1:850, or 1:750 to 1:800.

[0061] The photosensitive resin composition may further contain at least one additive selected from malonic acid, 3-amino-1,2-propanediol, a coupling agent containing a vinyl group or a (meth)acryloxy group, and a radical polymerization initiator in order to prevent stains and spots during application, improve leveling performance, and prevent the generation of residues due to undevelopment.

[0062] The additives contained therein can be easily adjusted depending on the desired physical properties.

[0063] The coupling agent may be a silane-based coupling agent. Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, gamma methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma isocyanatepropyltriethoxysilane, gamma glycidoxypropyltrimethoxysilane, beta epoxycyclohexyl, ethyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.

[0064] Specifically, the silane coupling agent can be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

[0065] In addition, the photosensitive resin composition may contain other additives such as antioxidants and stabilizers in a certain amount within a range that does not impair the physical properties.

[0066] The additives are preferably contained in an amount of 0.01 to 5% by weight, more preferably 0.01 to 2% by weight, based on the total weight of the photosensitive resin composition, and if the amount is outside the above range, it is undesirable because it may cause a problem of foreign matter being generated after development.

[0067] (B) Binder resin The photosensitive resin composition may include a binder resin, and the binder resin may include an acrylic binder resin.

[0068] An acrylic resin is a resin that contains one or more repeating acrylics as a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith.

[0069] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, specific examples of which include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0070] The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight, based on the total amount of the acrylic binder resin.

[0071] Examples of the second ethylenically unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; vinyl carboxylic acid ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These may be used alone or in combination of two or more.

[0072] Specific examples of acrylic resins include (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto. These may be used alone or in combination of two or more kinds.

[0073] The binder resin may include an epoxy-based binder resin.

[0074] The binder resin can improve heat resistance by further containing an epoxy-based binder resin. Examples of the epoxy-based binder resin include, but are not limited to, phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, and combinations thereof.

[0075] Furthermore, the binder resin including the epoxy-based binder resin ensures the dispersion stability of colorants such as pigments described below, and also helps to form pixels with a desired resolution during the development process.

[0076] The epoxy-based binder resin may be included in an amount of 1 wt% to 10 wt%, for example, 5 wt% to 10 wt%, based on the total amount of the binder resin. When the epoxy-based binder resin is included in the above range, the film remaining rate and chemical resistance may be significantly improved.

[0077] The epoxy equivalent weight of the epoxy-based binder resin may be 150 g / eq to 200 g / eq. When an epoxy-based binder resin having an epoxy equivalent weight within the above range is included in the binder resin, there is a beneficial effect on improving the degree of hardening of the formed pattern and on the fixation of the colorant in the structure on which the pattern is formed.

[0078] The binder resin may be dissolved in a solvent as a solid to form a photosensitive resin composition, as described below. In this case, the binder resin in the solid form may be about 10% by weight to 50% by weight, for example, 20% by weight to 40% by weight, based on the total amount of the binder resin solution dissolved in the solvent.

[0079] The binder resin may be included in an amount of 1% by weight to 20% by weight, specifically 1% by weight to 15% by weight, for example, 1% by weight to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, excellent developability and improved crosslinking properties can be obtained during the production of a color filter, resulting in excellent surface smoothness.

[0080] (C) Photopolymerizable compound As the photopolymerizable compound, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond can additionally be used.

[0081] The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can undergo sufficient polymerization upon exposure in the pattern formation step, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0082] Specific examples of the photopolymerizable compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ) acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy(meth)acrylate, and the like.

[0083] Examples of commercially available photopolymerizable compounds are as follows. Examples of monofunctional esters of (meth)acrylic acid include ARONIX (registered trademark) M-101, M-111, M-114, etc., manufactured by Toa Gosei Co., Ltd., KAYARAD (registered trademark) TC-110S, Copper TC-120S, etc., manufactured by Nippon Kayaku Co., Ltd., and V-158, V-2311, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples of bifunctional esters of (meth)acrylic acid include ARONIX (registered trademark) M-210, M-240, M-6200, etc., manufactured by Toa Gosei Co., Ltd., KAYARAD (registered trademark) HDDA, HX-220, R-604, etc., manufactured by Nippon Kayaku Co., Ltd., and V-260, V-312, V-335HP, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include ARONIX (registered trademark) M-309, M-400, M-405, M-450, M-710, M-8030, M-8060, etc. manufactured by Toyo Gosei Co., Ltd., KAYARAD (registered trademark) TMPTA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. manufactured by Nippon Kagaku Co., Ltd., and V-295, V-300, V-360, V-GPT, V-3PA, V-400, etc. manufactured by Osaka Organic Chemical Industry Co., Ltd. These products can be used alone or in combination of two or more kinds.

[0084] The photopolymerizable compound may be treated with an acid anhydride or modified with ethylene oxide to provide better developability.

[0085] The photopolymerizable compound can be contained in an amount of 1 to 20% by weight, specifically 1 to 4% by weight, for example 1 to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above range, curing upon exposure in the pattern formation process occurs sufficiently, resulting in excellent reliability and excellent developability in an alkaline developer.

[0086] (D) Photopolymerization initiator The photopolymerization initiator can be an initiator generally used in photosensitive resin compositions, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof.

[0087] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-mopolypropan-1-one, 2-benzyl-2-dimethylamino-1-(4-mopolyphenyl)-butan-1-one, and the like.

[0088] Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0089] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0090] Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0091] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, azine, 2-bipenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

[0092] Examples of oxime compounds that can be used include O-acyloxime compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0093] As the photopolymerization initiator, in addition to the above compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, etc. can be used.

[0094] Photoinitiators can also be used in conjunction with photosensitizers, which absorb light, become suspended in it, and then transfer that energy to initiate a chemical reaction.

[0095] Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0096] The photopolymerization initiator may be included in an amount of 0.1 to 5% by weight, specifically 0.3 to 4% by weight, for example 0.5 to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing during exposure in the pattern formation process occurs sufficiently, excellent reliability can be obtained, the pattern has excellent heat resistance, light resistance, and chemical resistance, and also has excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiator can be prevented.

[0097] (E) Coloring agent The photosensitive resin composition of one embodiment may contain a pigment as a colorant.

[0098] As the pigment, a red pigment, a purple pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, etc. can be used.

[0099] As the red pigment, in the Color Index, CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, etc. can be used, and these can be used alone or in combination of two or more types, but are not necessarily limited to these.

[0100] As the purple pigment, in the Color Index, CI Violet Pigment 23 (V.23), CI Violet Pigment 29, Dioxazine Violet, Fast Violet B, Methyl Violet Lake, Indanthrene Brilliant Violet, etc. can be used, and these can be used alone or in combination of two or more kinds, but are not necessarily limited to these.

[0101] As the green pigment, in the Color Index, CI Green Pigment 7, CI Green Pigment 36, CI Green Pigment 58, CI Green Pigment 59, etc. can be used, and these can be used alone or in combination of two or more kinds, but are not necessarily limited thereto.

[0102] The blue pigment may be, in the Color Index, a copper phthalocyanine pigment such as CI Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3, CI Blue Pigment 15:4, CI Blue Pigment 15:5, CI Blue Pigment 15:6, CI Blue Pigment 16, etc., which may be used alone or in combination of two or more kinds, but is not necessarily limited thereto.

[0103] As the yellow pigment, in the Color Index, an isoindolylene pigment such as CI Yellow Pigment 185, CI Yellow Pigment 139, etc., a quinophthalone pigment such as CI Yellow Pigment 138, etc., a nickel complex pigment such as CI Yellow Pigment 150, etc. can be used, and these can be used alone or in combination of two or more kinds, but are not necessarily limited to these.

[0104] As the black pigment, aniline black, parylene black, titanium black, carbon black, etc., which are listed in the Color Index, can be used alone or in combination of two or more kinds, but are not necessarily limited thereto.

[0105] Specifically, the colorant can include a blue pigment, a violet pigment, or a combination thereof to achieve the blue color, and more specifically, the pigment can be a mixture of blue and violet pigments in a weight ratio of 95:5 to 60:40, 90:10 to 70:30, or 85:15 to 75:25.

[0106] The pigment can be contained in the near infrared water-absorbing resin composition in the form of a dispersion.

[0107] Such a pigment dispersion may consist of a pigment, a solvent, a dispersant, a dispersing resin, and the like.

[0108] As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used, and among these, propylene glycol methyl ether acetate is preferably used.

[0109] The dispersant helps the pigment to be uniformly dispersed in the dispersion liquid, and all of the nonionic, anionic, and cationic dispersants can be used. Specifically, polyalkylene glycols or their esters, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylates, carboxylates, alkylamide alkylene oxide adducts, alkylamines, etc. can be used alone or in combination of two or more kinds.

[0110] The dispersing resin can be an acrylic resin containing a carboxy group, which can not only improve the stability of the pigment dispersion liquid, but also improve the patterning of pixels.

[0111] The colorant may include a pigment and a dye, and in this case, the resin composition of the embodiment may be a hybrid composition. In addition, the dye may include, but is not limited to, a metal complex dye.

[0112] The metal complex dye may be a compound having a maximum absorbance in the wavelength region of 200 nm to 650 nm. In order to match the color coordinates with the combination of dyes, any metal complex dye of any color that is soluble in an organic solvent may be used as long as it is a compound having an absorbance in the above range.

[0113] Specifically, the metal complex dye may be a green dye having a maximum absorbance in the wavelength region of 530 nm to 680 nm, a yellow dye having a maximum absorbance in the wavelength region of 200 nm to 400 nm, an orange dye having a maximum absorbance in the wavelength region of 300 nm to 500 nm, a red dye having a maximum absorbance in the wavelength region of 500 nm to 650 nm, or a combination thereof.

[0114] The metal complex dye may be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfur dye, a reduction dye, an azoic dye, a disperse dye, a reactive dye, an oxidation dye, an oil-soluble dye, an azo dye, an anthraquinone dye, an indigoid dye, a carbonium ion dye, a phthalocyanine dye, a nitro dye, a quinoline dye, a cyanine dye, a polymethine dye, or a combination thereof.

[0115] The metal complex dye may contain at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

[0116] Metal complex dyes include CI solvent dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35, and CI acid dyes such as CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 51, 58, 63, 65, 80, 104, 105, 106, and 109. dyes, CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc., CI Direct Dyes, CI Basic Green 1, etc., CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, At least one selected from the group consisting of CI Mordant dyes such as CI Pigment Green 7, 36, 58, green pigments such as CI Pigment Green 7, 36, 58, Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, Solvent Red 32, Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132, and Solvent Red 218 and a complex of the metal ion can be used.

[0117] The dye containing a metal complex may have a solubility of 5 or more in a solvent used in the photosensitive resin composition according to an embodiment, i.e., a solvent described below, and specifically may be 5 to 10. The solubility may be obtained from the amount (g) of the dye dissolved in 100 g of solvent. When the solubility of the dye containing a metal complex is within the above range, compatibility with other components constituting the photosensitive resin composition according to an embodiment and coloring power can be ensured, and precipitation of the dye can be prevented.

[0118] The solvent may be, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or a combination thereof.

[0119] By having the specific range, the compound can be effectively used in color filters of LCDs, LEDs, etc., which exhibit high luminance and high contrast ratio at desired color coordinates.

[0120] The dye containing a metal complex may be included in an amount of 0.01 to 1% by weight, for example, 0.01 to 0.5% by weight, based on the total weight of the photosensitive resin composition. When the dye containing a metal complex is used in the above range, high brightness and light-to-dark ratio can be achieved with desired color coordinates.

[0121] When the dye and the pigment are mixed, they can be mixed at a weight ratio of 0.1:99.9 to 99.9:0.1, specifically, at a weight ratio of 1:9 to 9:1. When mixed within this weight ratio range, it is possible to control the chemical resistance and maximum absorption wavelength within an appropriate range, and to achieve high brightness and light-dark ratio at the desired color coordinates.

[0122] The colorant may be contained in an amount of 5% by weight to 70% by weight, specifically 6% by weight to 50% by weight, for example 7% by weight to 30% by weight, based on the total amount of the photosensitive resin composition. When the colorant is contained within the above range, the coloring effect and developability are excellent.

[0123] (F) Solvent The solvent may be a material that is compatible with, but does not react with, the additives, the binder resin, the photopolymerizable compound, the photopolymerization initiator, and the colorant.

[0124] Examples of the solvent include alcohols such as methanol and ethanol, ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran, alkyl acetates such as ethyl acetate and butyl acetate, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate, carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone. ketones such as methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters such as methyl lactate, ethyl lactate, etc.; oxyacetate alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetate alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxypropionic acid methyl, 3-oxypropionic acid alkyl esters such as ethyl 3-oxypropionate, 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionate, methyl 3-ethoxypropionate, 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate,2-alkoxypropionic acid alkyl esters such as methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; and ketone acid esters such as ethyl benzoate, and high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0125] Of these, in consideration of common use and reactivity, preferably, ketones such as cyclohexanone, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, esters such as ethyl 2-hydroxypropionate, carbitols such as diethylene glycol monomethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone can be used.

[0126] Specifically, the solvent may include two or more solvents having different boiling points. The "boiling point" of a liquid substance is the temperature at which the vapor pressure of the liquid substance becomes equal to the external pressure and the liquid substance starts to boil, and it varies depending on the external pressure. In one embodiment, the boiling point is below 1 atm.

[0127] In one embodiment, the photosensitive resin composition contains two solvents having different boiling points, and thus the volatilization rate and volatilization position of the solvent can be harmoniously controlled during the process of coating the photosensitive resin composition on a substrate or a lower photosensitive resin film, and the solvent volatilization can be mainly performed on the surface of the coating rather than the bottom, thereby improving the filling characteristics, surface roughness, etc.

[0128] For example, the solvent may contain two or more of the following solvents: propylene glycol monomethyl ether acetate (PGMEA), n-butyl alcohol (n-BA), and diethylene glycol methyl ethyl ether (MEDG). Of course, the solvent may contain all three solvents, in which case the synergistic effect is the highest.

[0129] The solvent may be contained in the remaining amount, for example, 30% to 60% by weight, for example, 40% to 50% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has excellent coatability, and a coating film with excellent flatness can be obtained.

[0130] The photosensitive resin composition can be used as a photosensitive resin composition for a color filter of a CMOS image sensor, specifically, as a photosensitive resin composition for a blue color filter of a CMOS image sensor.

[0131] (Photosensitive resin film, color filters and CMOS image sensors) In another embodiment, a photosensitive resin film produced using the photosensitive resin composition is provided.

[0132] In another embodiment, there is provided a color filter produced using the photosensitive resin composition.

[0133] In another embodiment, a CMOS image sensor including a color filter is provided.

[0134] The color filter is manufactured in the following manner.

[0135] The above-mentioned photosensitive resin composition is applied to a glass substrate by a suitable method such as spin coating, roller coating, spray coating, etc., to a suitable thickness to form a photosensitive resin composition layer.

[0136] Next, the substrate on which the photosensitive resin composition layer is formed is irradiated with light so as to form a pattern required for the color filter. As the light source used for irradiation, UV, electron beams, or X-rays can be used, and for example, UV in the 190 nm to 450 nm range, specifically, 200 nm to 400 nm range can be irradiated. In the irradiating step, a photoresist mask can also be used. After performing the irradiating step in this way, the photosensitive resin composition layer irradiated with the light source is treated with a developer. At that time, the non-exposed part is dissolved from the photosensitive resin composition layer, thereby forming a pattern required for the color filter. By repeating such a step according to the number of required colors, a color filter having a desired pattern can be obtained. In addition, in the above-mentioned step, if the image pattern obtained by development is reheated or cured by irradiation with active rays, etc., crack resistance, solvent resistance, etc. can be improved.

[0137] The present invention will be described in more detail with reference to the following examples. However, the following examples are preferred embodiments of the present invention and the present invention is not limited to the following examples.

[0138] (Production of Photosensitive Resin Composition) (Examples 1 to 9 and Comparative Examples 1 to 6) Photosensitive resin compositions were prepared by mixing the ingredients in the compositions shown in Tables 1 to 3.

[0139] Specifically, a photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, and then a binder resin was added thereto and stirred at room temperature for 60 minutes. Next, a photopolymerizable compound and a colorant (pigment dispersion) were added to the obtained reaction product and stirred at room temperature for 30 minutes. Additionally, additives were added and stirred at room temperature for 30 minutes. Next, the product was filtered twice to remove impurities, thereby producing a photosensitive resin composition.

[0140] [Table 1]

[0141] [Table 2]

[0142] [Table 3]

[0143] In Tables 1 to 3, the components used are as follows:

[0144] (A) Additives (A-1) Dilute solution (dispersion medium: PGMEA) of fluorosurfactant (product name: F-556, manufacturer: DIC) (A-2) Dilute solution of fluorosurfactant (product name: F-553, manufacturer: DIC) (dispersion medium: PGMEA) (A-3) Silane coupling agent (product name: KBM-503, manufacturer: Shinetsu)

[0145] (B) Binder resin (B-1) Dispersion of acrylic binder resin (product name: RY-92, manufacturer: Showa Denko, weight average molecular weight: 5,000 to 20,000 g / mol, acid value: 30 to 180 KOHmg / g) (solvent: PGMEA)

[0146] (C) Photopolymerizable compound (C-1) Dipentaerythritol hexaacrylate (DPHA, Manufacturer: Nippon Kayaku)

[0147] (D) Photopolymerization initiator (D-1) Oxime initiator (product name: SPI-03, manufacturer: Sanyosha)

[0148] (E) Coloring agent (E-1) Mixed pigment dispersion of B15:6 and V23 (solvent: PGMEA)

[0149] (F) Solvent (F-1) Propylene glycol monomethyl ether acetate (PGMEA, boiling point: 146.4°C, manufacturer: Sigma-Aldrich) (F-2) n-Butyl alcohol (n-BA, boiling point: 117.7°C @ 1 atm, manufacturer: Sigma-Aldrich)

[0150] (Evaluation Example 1: Viscosity of Photosensitive Resin Composition) At 25° C., 4 g of each of the photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 6 was applied, and the viscosity was evaluated using a rheometer. The evaluation results are shown in Table 4.

[0151] [Table 4]

[0152] (Evaluation example 2: Surface characteristics of color filters) (1) Surface roughness The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 6 were coated on an 8-inch Si substrate using a spin coater (Opticoat MS-A150, manufactured by Mikasa Corp.), followed by soft-baking at 100°C for 180 seconds using a hot plate, and then exposed to light for 1000 msec using an i-line stepper (NSR-2005i10C, manufactured by Nikon Corp.). Exposure was performed on the areas indicated by squares in FIG. 1.

[0153] The exposed substrate was developed with 0.19% TMAH aqueous solution at room temperature using the spray & puddle method, and then hard-baked on a hot plate at 200°C for 5 minutes, resulting in a color filter specimen with a 5000 Å thick photosensitive resin film formed on the Si substrate.

[0154] For each of the obtained color filter test pieces, an image was taken at a magnification of 200 times using a microscope (model name: BX51, manufacturer: Olympus). After shading the taken image, the surface roughness of the second square area from the right was visually confirmed, and the surface was rated as "good" if it was not rough, "bad" if it was rough, and "very bad" if it was very rough, and these are shown in Table 5 below.

[0155] (2) Checkered surface For each color filter test piece obtained above, the checkered pattern was visually confirmed, and the results were rated as "good" if the checkered pattern was clearly distinguishable, "poor" if the checkered pattern was indistinctly distinguishable, and "very poor" if the checkered pattern was not distinguishable, and are listed in Table 5 below.

[0156] (3) Thickness For each of the color filter test pieces obtained above, a thickness profile of 1000 μm was measured at a scanning speed of 50 μm / s using a thickness meter (model name: P-16, manufacturer: KLA), and the measurement results are shown in Figure 2.

[0157] [Table 5]

[0158] Comprehensively evaluating Tables 4 and 5, it can be seen that the viscosity of the photosensitive resin composition varies depending on the content of the leveling agent, and in particular, only when the leveling agent is contained in an amount of 15 ppm to 30 ppm in the total amount of the photosensitive resin composition can the surface roughness and lattice fringes of the color filter test specimen be improved.

[0159] Accordingly, the leveling agent is used, and its content is optimized to be 15 ppm to 30 ppm in the total amount of the photosensitive resin composition, so that the photosensitive resin composition can be uniformly coated on the substrate or the lower photosensitive resin film.

[0160] Furthermore, the photosensitive resin film and color filter produced using the photosensitive resin composition of one embodiment represented by Examples 1 to 9 have excellent surface smoothness, and can contribute to realizing a certain level of image quality of the image sensor.

[0161] Although the above describes a preferred embodiment of the present invention, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the attached drawings, and of course, fall within the scope of the present invention.

Claims

1. (A) a leveling agent, (B) a binder resin, (C) photopolymerizable compound, (D) a photopolymerization initiator, (E) a colorant, and (F) a photosensitive resin composition including a solvent, the leveling agent includes a nonionic fluorine-based surfactant and is included in an amount of 15 ppm to 30 ppm based on the total amount of the photosensitive resin composition; The solvent includes propylene glycol monomethyl ether acetate (PGMEA) and n-butyl alcohol (n-BA), and the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1 , wherein the leveling agent is contained in an amount of 20 ppm to 25 ppm based on the total composition.

3. The photosensitive resin composition according to claim 1 , further comprising a leveling agent dilution liquid for dispersing the leveling agent.

4. The photosensitive resin composition according to claim 3 , wherein the leveling agent is contained in an amount of 1% by weight to 20% by weight in the total amount of the leveling agent and the diluted leveling agent.

5. The photosensitive resin composition according to claim 1 , further comprising a coupling agent containing a (meth)acryloxy group.

6. The photosensitive resin composition according to claim 1 , wherein the binder resin comprises an acrylic binder resin.

7. The photosensitive resin composition of claim 1 , wherein the colorant comprises a blue pigment, a violet pigment, or a combination thereof.

8. The photosensitive resin composition according to claim 1 , wherein the solvent comprises two or more solvents having different boiling points.

9. The photosensitive resin composition contains, relative to the total amount of the photosensitive resin composition, The leveling agent (A) is 15 ppm to 30 ppm, The (B) binder resin is 1% by weight to 20% by weight, The (C) photopolymerizable compound is 1% by weight to 20% by weight, The (D) photopolymerization initiator is 0.1% by weight to 5% by weight, The (E) colorant is 5% by weight to 70% by weight, and The (F) solvent The photosensitive resin composition according to claim 1 ,

10. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a viscosity of 1.5 cP to 3.8 cP at 25°C.

11. A photosensitive resin film produced by using the photosensitive resin composition according to any one of claims 1 to 10.

12. A color filter comprising the photosensitive resin film of claim 11.

13. A CMOS image sensor comprising the color filter of claim 12.

Images