WO2011002247A2 - 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 고체 촬상 소자 - Google Patents
300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 고체 촬상 소자 Download PDFInfo
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- WO2011002247A2 WO2011002247A2 PCT/KR2010/004288 KR2010004288W WO2011002247A2 WO 2011002247 A2 WO2011002247 A2 WO 2011002247A2 KR 2010004288 W KR2010004288 W KR 2010004288W WO 2011002247 A2 WO2011002247 A2 WO 2011002247A2
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
Definitions
- the present invention relates to a colored photosensitive resin composition for producing a color filter of a solid-state imaging device using an ultra-short wavelength exposure machine of 300 nm or less, a color filter using the same, and a solid-state imaging device including the same.
- an image pickup device for implementing a color image is provided with a color filter on an upper portion of a light sensing portion that receives and receives light from the outside to generate and accumulate photocharges.
- the color filter may be composed of a coloring pattern of three colors of red, green, and blue, or a coloring pattern of three colors of yellow, magenta, and cyan. Is done.
- the coloring pattern of each said color filter is formed using the coloring photosensitive resin composition containing a pigment or dye.
- Colored pattern processing using the colored photosensitive resin composition is usually performed in a lithography process.
- the wavelength of the light source for the lithography process used to manufacture the colored pattern is a g-line (wavelength 436nm) or i-line (wavelength 365nm) wavelength.
- solid-state imaging devices such as digital cameras require that the pixel size is reduced to less than 2um from the existing 4-5um in order to improve the high pixel quality and image quality, and the coloring pattern is also required to have ultrafine and square.
- the inventors of the present invention conducted an ultra miniaturization of the color pattern size of the color filter for a solid-state image sensor using an ultra short wavelength exposure machine of 300 nm or less.
- the conventional colored photosensitive resin composition is hardly curable at an ultra short wavelength of 300 nm or less. There was a problem that it does not work well.
- the curing is made at ultra-short wavelength of less than 300nm, there was a problem that the sensitivity and resolution falls.
- the present invention provides a color filter for color filter manufacturing of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less, which enables formation of a high-resolution ultrafine colored pattern when manufacturing a color filter for a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less. Its purpose is to provide a photosensitive resin composition.
- the present invention exhibits high sensitivity even when a small amount of photoinitiator is used, and thus coloration for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less, which allows formation of a high resolution ultra-fine colored pattern even at a low exposure amount.
- Another object is to provide a photosensitive resin composition.
- the present invention provides a coloring photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure apparatus of 300 nm or less, which exhibits high sensitivity and is capable of forming a high-resolution ultrafine colored pattern having excellent line characteristics even at a low exposure amount.
- a coloring photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure apparatus of 300 nm or less, which exhibits high sensitivity and is capable of forming a high-resolution ultrafine colored pattern having excellent line characteristics even at a low exposure amount.
- Another object of the present invention is to provide a color filter having a high-resolution ultra-fine colored pattern formed using the colored photosensitive resin composition.
- Another object of the present invention is to provide a solid-state image sensor including the color filter.
- the present invention provides a coloring photosensitive resin composition
- a coloring photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerization initiator comprises a compound reacting at 300 nm or less. It provides the coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less.
- the photopolymerization initiator may be at least one selected from the group consisting of acetophenone-based, benzophenone-based, thioxanthone-based, and triazine-based photopolymerization initiators. More preferably, the photopolymerization initiator may be at least one selected from the group consisting of acetophenone-based and benzophenone-based photopolymerization initiators.
- the photoinitiator is at least one selected from the group consisting of acetophenone-based, benzophenone-based, thioxanthone-based and triazine-based photopolymerization initiators
- the photopolymerization initiator is 5 to 20% by weight relative to the solid content in the colored photosensitive resin composition. It is preferable to contain%.
- the photopolymerization initiator may be an oxime ester-based photopolymerization initiator.
- the photopolymerization initiator is an oxime ester photopolymerization initiator
- the photopolymerization initiator is preferably contained in a weight fraction of 1 to 20% by weight based on the solid content in the colored photosensitive resin composition.
- the photopolymerization initiator may include an oxime ester photopolymerization initiator, and may further include a photopolymerization initiator other than the oxime ester photopolymerization initiator.
- the other photopolymerization initiator is preferably at least one selected from the group consisting of an active radical generator, a sensitizer and an acid generator selected from acetophenone-based, benzophenone-based, thioxanthone-triazine-based or benzoin-based photopolymerization initiators.
- the oxime ester-based photoinitiator is preferably contained 1 to 99% by weight based on the total weight of the photopolymerization initiator including the same, the photoinitiator is 1 to 50% by weight relative to the solid content in the colored photosensitive resin composition It is preferable to contain%.
- the ultra-short wavelength exposure machine of 300 nm or less is a KrF scanner exposure machine (248 nm).
- the present invention provides a colored pattern formed by coating the colored photosensitive resin composition according to the present invention on a substrate and then exposing and developing in a predetermined pattern using an ultra-short wavelength exposure machine of 300 nm or less. It provides a color filter comprising a.
- the exposure machine is preferably a KrF scanner exposure machine (248 nm).
- the exposure amount at the time of the said exposure was made 200 mJ / cm ⁇ 2> or less.
- the present invention provides a solid-state imaging device comprising the color filter.
- the coloring photosensitive resin composition according to the present invention includes a photopolymerization initiator reacting at an ultrashort wavelength of 300 nm or less, and thus, a fine colored pattern of high resolution when exposed using an ultrashort wavelength exposure machine of 300 nm or less in the process of manufacturing a color filter. Can be implemented.
- the photopolymerization initiator comprises at least one selected from the group consisting of acetophenone-based, benzophenone-based, thioxanthone-based and triazine-based photopolymerization initiators reacting at ultra-short wavelengths of 300 nm or less
- conventional colored photosensitive resin compositions In the process of manufacturing the color filter using an excessive amount compared to the use of an ultra-short wavelength exposure device of less than 300nm can implement a fine color pattern of high resolution during exposure.
- the photopolymerization initiator contains an oxime ester photopolymerization initiator that reacts at an ultra-short wavelength of 300 nm or less, even when a small amount of photoinitiator is used, high sensitivity is exhibited even when a small amount of photoinitiator is used to form a high-resolution ultrafine colored pattern with a small exposure amount. It is possible.
- the photopolymerization initiator includes an oxime ester photopolymerization initiator reacting at an ultra-short wavelength of 300 nm or less and other photopolymerization initiators, it is possible to form a high resolution ultrafine colored pattern having excellent line characteristics even at a very small exposure amount.
- the colored pattern may have a fine size of 1.4 ⁇ m or less, particularly 1.0 ⁇ m or less. Accordingly, the color filter may be usefully used for a solid state imaging device.
- FIG. 6 is a graph showing the appropriate exposure amount according to the content of the oxime ester-based photoinitiator according to Examples 6 to 9 of the present invention.
- the coloring photosensitive resin composition (henceforth simply called “coloring photosensitive resin composition") of the color filter manufacture of the solid-state image sensor using the ultra-short wavelength exposure machine of 300 nm or less which concerns on this invention is a coloring agent (A), binder resin (B), and a photopolymerizable compound. (C), a photoinitiator (D), and a solvent (E).
- the colorant may be an organic or inorganic pigment, preferably an organic pigment may be used in consideration of heat resistance and development.
- Each pigment can be used individually or in combination of 2 or more types.
- organic pigments may be finely granulated by rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced therein, graft treatment on the surface of the pigment using a polymer compound, sulfuric acid fine granulation method, or the like. Treatment or washing treatment with an organic solvent, water or the like can be performed to remove impurities.
- the pigment examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Specifically, the pigment may be a color index (The Society of Dyers and Colourists). Compounds classified as pigments can be used.
- pigments that can be used include,
- C.I. Pigment Yellow No. 1 C.I. Pigment Yellow 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No.
- the usage-amount of the said coloring agent is 5 weight%-60 weight%, Preferably it is 10 weight%-50 weight% with respect to solid content in a coloring photosensitive resin composition.
- amount of the coloring agent is included in the above range on the basis of the above standard, when the color filter is manufactured, the color density of the coloring pattern is sufficient, and the coloring pattern with sufficient mechanical strength can be formed.
- the colorant may be used in the form of a dispersion liquid (hereinafter sometimes referred to as a mill base), which is previously mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes 0.2 ⁇ m or less.
- the dispersion may be dispersed by further adding a pigment dispersant in the dispersion process, or may be dispersed by blending a part or all of the binder resin.
- the colorant is preferably contained 5 to 60 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the total dispersion.
- the pigment dispersant may be, for example, a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a cationic surfactant, an anionic surfactant, or a nonionic interface.
- An activator etc. can be used, These can be used individually or in combination of 2 or more types, respectively.
- surfactants may be used as the pigment dispersant.
- examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, and sorbitan fatty acid esters. , Fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like, as well as trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.).
- EFTOP manufactured by Tochem Products
- MEGAFAC manufactured by Dainippon Ink & Chemicals Co., Ltd.
- Florad manufactured by Sumitomo 3M
- Surflon above, manufactured by Asahi Glass Co., Ltd.
- SOLSPERSE manufactured by Genka Corp.
- EFKA manufactured by EFKA Chemicals Co., Ltd.
- PB 821 manufactured by Ajinomoto Co., Ltd.
- the pigment dispersant is preferably 0.01 to 1 parts by weight, preferably 0.05 to 0.5 parts by weight based on 1 part by weight of the colorant, in consideration of dispersion of the colorant.
- Solid content in a coloring photosensitive composition in this invention means the sum total of the component which removed the solvent.
- the binder resin serves as a binder resin for the colorant, and any binder may be used as long as the polymer is soluble in the alkaline developer used in the developing step.
- binder resin examples include copolymers of carboxyl group-containing monomers and other monomers copolymerizable with the carboxyl group-containing monomers.
- carboxyl group-containing monomer For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has 1 or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. Can be mentioned.
- unsaturated monocarboxylic acid acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.
- unsaturated dicarboxylic acid a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.
- the unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride.
- the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate mono (2-acryloyloxyethyl), monosuccinate mono (2-methacryloyloxy Ethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), and the like.
- the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate. have.
- carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.
- the other monomer copolymerizable with the carboxyl group-containing monomer is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyltoluene.
- copolymer examples include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacryl Acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methylmethacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / methylmethacrylate / methacryl Acid / styrene copolymer etc. are mentioned.
- the content of the monomer unit having a carboxyl group is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight. If content of the said carboxyl group-containing monomeric unit is in the said range, since solubility with respect to a shape liquid is favorable and the coloring pattern at the time of image development is preferable, it is preferable.
- the binder resin preferably has an acid value in the range of 20 to 200 (mgKOH / g).
- the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.
- the binder resin preferably has a weight average molecular weight (MW) of 5000 to 400000, or 10000 to 300000, as measured by gel permeation chromatography (GPC) using polystyrene as a standard material.
- MW weight average molecular weight
- GPC gel permeation chromatography
- the binder resin is preferably contained in a weight fraction of 5% by weight to 85% by weight, preferably 20% by weight to 70% by weight relative to the solid content in the colored photosensitive resin composition.
- the binder resin is within the content range on the basis of the reference, the formation of the pattern is possible, and the resolution and the residual film ratio are improved.
- the said photopolymerizable compound is a compound which can be superposed
- the compound which has a polymerizable carbon-carbon unsaturated bond, etc. are mentioned.
- Such compounds may be monofunctional photopolymerizable compounds, bifunctional photopolymerizable compounds, or trifunctional or higher polyfunctional photopolymerizable compounds.
- Examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl. Pyrrolidone etc. are mentioned.
- bifunctional photopolymerizable compound examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentane Diol dimethacrylate etc. are mentioned.
- trifunctional or higher polyfunctional photopolymerizable compound examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate
- pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned.
- the photopolymerizable compounds exemplified above may be used alone or in combination of two or more thereof. It is preferable to use the bifunctional or more photopolymerizable compound among the said photopolymerizable compounds.
- the amount of the photopolymerizable compound used is 0.1 to 70% by weight, preferably 1 to 60% by weight, based on the weight of solids in the colored photosensitive resin composition.
- strength or smoothness of a coloring pattern will become favorable.
- the photopolymerization initiator may be used to improve the physical properties of the ultrafine colored pattern to be implemented, as well as the content for implementing the ultrafine colored pattern. This will be described in more detail below.
- the photopolymerization initiator may be used without limitation so long as it is capable of polymerizing the binder resin and the photopolymerizable compound by generating an active radical or generating an acid in response to an ultrashort wavelength of 300 nm or less.
- the photopolymerization initiator may include at least one selected from the group consisting of acetophenone-based, benzophenone-based, thioxanthone-based, and triazine-based photopolymerization initiators. More preferably, the photopolymerization initiator may be at least one selected from the group consisting of acetophenone-based and benzophenone-based photopolymerization initiators.
- acetophenone-based photoinitiator is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [2- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -On oligomers, etc. are mentioned.
- benzophenone-based photopolymerization initiator examples include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.
- thioxanthone photopolymerization initiator examples include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4- Propoxy thioxanthone etc. are mentioned.
- triazine photoinitiator examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (
- the photopolymerization initiator is more than the amount used in the conventional colored photosensitive resin composition. Only in excess, a sufficiently fine colored pattern can be obtained.
- the photopolymerization initiator may be contained in a weight fraction of 5 to 20% by weight, more preferably 10 to 20% by weight relative to the solid content in the colored photosensitive resin composition.
- the photoinitiator is less than 5% by weight based on the above standards, there is a problem in that the sensitivity at the wavelength of 300 nm or less is not obtained to obtain an ultra finely colored pattern with excellent resolution. Therefore, it is preferable to use a photoinitiator within the said range.
- the photopolymerization initiator may be an oxime ester-based photopolymerization initiator.
- oxime ester photopolymerization initiator examples include 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime)) and 1- (4-methylsulfanyl-phenyl) -butane -1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl ) -Ethyl acetate-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl- 4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) etc. are mentioned.
- the illustrated oxime ester photoinitiators can be used alone or in combination of two or more.
- the photoinitiator when an oxime ester photoinitiator is used, it reacts with high sensitivity to an ultra-short wavelength of 300 nm or less even with a small amount, thereby enabling the implementation of an ultrafine colored pattern even with a small exposure amount.
- the photopolymerization initiator is an oxime ester photopolymerization initiator
- the photopolymerization initiator is preferably contained in a weight fraction of 1 to 20% by weight based on the solid content in the colored photosensitive resin composition.
- the oxime ester-based photoinitiator is less than 1% by weight based on the above standards, there is a problem in that the sensitivity at the wavelength of 300 nm or less is reduced and an ultrafine colored pattern with excellent resolution cannot be obtained. Since there is a problem that improved high sensitivity properties cannot be obtained, it is preferable to use a photopolymerization initiator within the above range.
- the photopolymerization initiator may include an oxime ester photopolymerization initiator, and may further include a photopolymerization initiator other than the oxime ester photopolymerization initiator.
- the other photopolymerization initiator is preferably at least one selected from the group consisting of an active radical generator, a sensitizer and an acid generator selected from acetophenone series, benzophenone series, thioxanthone series, triazine series or benzoin series photopolymerization initiators. .
- the oxime ester-based, acetophenone-based, benzophenone-based, thioxanthone-based, triazine-based photopolymerization initiator may be used as described above.
- benzoin-based photoinitiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
- sensitizer examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, titanocene compound and the like can also be used.
- Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Toluene sulfonate, diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned.
- onium salts such as 4-hydroxyphenyldimethylsulfonium p-tol
- the photoinitiator illustrated above can be used individually or in combination of 2 types or more, respectively.
- the photopolymerization initiator When the photopolymerization initiator is used by mixing an oxime ester photopolymerization initiator with another photopolymerization initiator other than the oxime ester photopolymerization initiator, it is possible to form an ultrafine colored pattern having excellent line characteristics.
- the oxime ester photoinitiator is 1 to 99% by weight based on the total amount of the photoinitiator including the same. % Is preferably included.
- the oxyester-based photoinitiator is less than 1% by weight based on the above standards, there is a problem in that the sensitivity is not obtained to obtain an ultra-fine colored pattern with excellent resolution, and when the content exceeds 99% by weight, the resolution is lowered. It is preferable to use an oxime ester type photoinitiator within the range.
- the said photoinitiator is contained 1-50 weight% in weight fraction with respect to solid content in a coloring photosensitive resin composition. If the photopolymerization initiator is less than 1% by weight, there is a problem in that the sensitivity at the wavelength of 300 nm or less is insufficient to obtain an ultra-fine colored pattern with excellent resolution, and if it exceeds 50% by weight, the resolution is deteriorated. It is preferable to use a photoinitiator within the said range.
- the photopolymerization initiator according to the present invention may be used together with a photopolymerization initiation aid to enhance the polymerization of the photopolymerizable compound.
- photoinitiation start adjuvant an amine photoinitiation start adjuvant, an alkoxy anthracene type photoinitiation start adjuvant, etc. are mentioned, for example.
- amine photopolymerization start adjuvant examples include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl4-dimethylaminobenzoate, ethyl4-dimethylaminobenzoate, isoamyl4-dimethylaminobenzoate, 2-dimethylamino Ethylbenzoate, 2-ethylhexyl4-dimethylaminobenzoate, N, N-dimethylp-toluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michaeller's ketone), 4, 4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned.
- alkoxy anthracene-based photopolymerization start adjuvant examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.
- the photopolymerization start adjuvant is used in such a content, it is preferable because the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter is improved.
- the solvent is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions can be used.
- the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like, and diethylene glycol dialkyl ethers such as diethylene glycol dimethyl.
- ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like
- diethylene glycol dialkyl ethers such as diethylene glycol dimethyl.
- Ethylene glycol alkyl ether acetates such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, such as methyl cellosolve acetate and ethyl cellosolve acetate, and alkylene glycol alkyl ether acetate
- aromatic hydrocarbons such as benzene, toluene, xylene and the like
- ketone For example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and the like, alcohols such as ethanol, propanol, butan
- the solvent is preferably contained 50% by weight to 90% by weight, preferably 60% by weight to 85% by weight based on the total amount of the colored photosensitive resin composition including the same.
- content of the solvent is included in the range of 50% by weight to 90% by weight, it is preferable because the coating property is good.
- the colored photosensitive resin composition may further include an additive as necessary.
- additives examples include fillers, polymers other than binder resins, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, organic acids, organic amino compounds, curing agents, and the like.
- the filler examples include glass, silica, alumina, and the like.
- Examples of the other polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.
- adhesion promoter examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, etc. are mentioned.
- antioxidants examples include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.
- UV absorber examples include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
- Examples of the aggregation inhibitor include sodium polyacrylate and the like.
- organic acid examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethylacetic acid, enanthic acid, caprylic acid, and the like.
- Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumene acid, hemelitic acid, mesitylene acid, etc., aromatic dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, etc., aromatic polycarboxylic acids such as trimellitic acid, Mount Trimes, Melopanic acid, pyromellitic acid and the like, and other acids.
- organic amino compounds include mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, s-butylamine, t-butyl amine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3- Methylcyclohexylamine, 4-methylcyclohexylamine and the like, di (cyclo) alkylamines such as methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, din-propylamine, dii- Propylamine, din-
- the curing agent may be used for the purpose of curing the colored pattern by post-development heat treatment in patterning to improve its mechanical strength.
- the compound which can crosslink a binder resin by reacting with the carboxyl group in a binder polymer by heating for example is mentioned, A coloring pattern is hardened by crosslinking a binder polymer.
- the compound which can be homopolymerized by heating can also be used, A color pixel etc. are hardened by homopolymerization.
- an epoxy compound, an oxetane compound, etc. are mentioned, for example.
- epoxy compound examples include epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, besphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, Brominated derivatives of these epoxy resins such as cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils; Aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof;
- the epoxidation material of the (co) polymer of butadiene, the epoxidation material of the (co) polymer of isoprene, the (co) polymer of glycidyl (meth) acrylate, a triglycidyl isocyanurate, etc. are mentioned.
- oxetane compound examples include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.
- the compound which can cause ring-opening polymerization of the epoxy group in an epoxy compound, and the oxetane skeleton in an oxetane compound can be used together.
- a compound polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively.
- polyhydric carboxylic acid examples include aromatic polyhydric carboxylic acids, such as phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimethyltriic acid, 1,4,5,8-naphthalenetetracarboxylic Aliphatic polyhydric carboxylic acids such as acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic Alicyclic polyhydric carboxylic acids such as acid, maleic acid, fumaric acid, itaconic acid, such as hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentane Tricarboxylic acid, 1,2,4-cyclohexanetric
- polyhydric carboxylic anhydride examples include aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and the like.
- Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvalyl anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic acid
- Alicyclic polyhydric carboxylic anhydrides such as dianhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexane Ester group-containing carboxylic acids such as tricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, nad anhydride radish It can include water, such as ethylene glycol bis trimellitic acid,
- the colored photosensitive resin composition of this invention which has said composition can be manufactured by the following method, for example.
- the coloring agent (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 ⁇ m or less.
- a pigment dispersant is used as needed and some or all of binder resin (B) may be mix
- Residual amount of binder resin (B), photopolymerizable compound (C) and photoinitiator (D), other components used if necessary, and additional solvents as necessary in the obtained dispersion hereinafter sometimes referred to as mill base).
- mill base When (E) is added and fully mixed, the coloring photosensitive resin composition which concerns on this invention can be obtained.
- the coloring photosensitive resin composition which has the composition mentioned above which concerns on this invention provides the color filter manufactured using.
- the method for manufacturing a color filter according to the present invention includes a coating film forming step of forming a coating film by coating the colored photosensitive resin composition according to the present invention on a substrate, and using microwaves in a region where a coloring pattern of the coating film is to be formed.
- the coating film forming step is to form a coating film by coating a colored photosensitive resin composition on a substrate, the substrate is a glass substrate, a silicon wafer and a plastic substrate such as polyethersulfone (PES) or polycarbonate (PC) It may be a plate and the like, the kind is not particularly limited.
- PES polyethersulfone
- PC polycarbonate
- the coating can be carried out using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (also called 'die coater'), inkjet, or the like.
- a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (also called 'die coater'), inkjet, or the like.
- the thickness at the time of coating can be formed in various thicknesses without limitation, it is preferable to coat at 0.5 ⁇ 1.0um, it is important to make the coating thickness uniform thickness over the entire surface.
- the thickness at the time of the coating is included in the above range, the surface smoothness of the coating film is excellent, and the curing is faster, thereby improving the production speed.
- volatile components such as solvents are removed through preliminary drying to obtain a coating film.
- the preliminary drying may be performed at 100 to 120 ° C. for 1 to 30 minutes.
- volatile components such as solvents are quickly removed to obtain a good dry coating film.
- the exposing step is a step of exposing an ultrashort wavelength laser of 300 nm or less to an area where a color pattern of the coating film is to be formed by using a mask.
- Lasers having a wavelength of less than 300 nm can mainly use known KrF (248 nm) scanners.
- the KrF scanner is an exposure machine in which a laser oscillated using a krypton fluoride source has a wavelength band of 248 nm.
- crosslinking and photocuring are caused by the photopolymerization initiator only at the portion where light is transmitted by the mask.
- the exposure is not necessarily limited, but the exposure dose is preferably 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 or less, and more preferably 50 to 150 mJ / cm 2.
- the exposure amount exceeds 300mJ / cm2 it has the disadvantage that it is possible to shorten the life of the exposure machine due to the increase of the overall process time due to the delay in the exposure process and the distortion of the lens inside the exposure machine.
- the developing step is a step of forming a colored pattern by removing the unexposed coating area in the exposing step.
- the developing solution used to remove the non-exposure end coating region in the developing step may be one commonly used in the art, and is usually an aqueous solution containing an alkaline compound and a surfactant.
- the alkaline compound contained in the developer may be any of inorganic and organic alkaline compounds.
- the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.
- organic alkaline compound examples include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.
- organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.
- concentration of the alkaline compound in the said developing solution is 0.01 to 10 weight%, More preferably, it is 0.03 to 5 weight%.
- nonionic surfactant As surfactant contained in the said developing solution, you may use any of a nonionic surfactant, anionic surfactant, or cationic surfactant.
- the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
- anionic surfactant examples include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; Alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate, etc. are mentioned.
- Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.
- the concentration of the surfactant in the developer may be 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.
- the color filter having a colored pattern may be subjected to post-heat treatment at 150 to 230 ° C. for about 1 minute to 60 minutes.
- the post-heat treatment is to completely remove the residual solvent on the pattern and to harden the embodied pattern.
- This invention provides the color filter manufactured by the manufacturing method of the color filter for solid-state image sensors mentioned above.
- the color filter has a finely colored coloring pattern as the ultrashort plate exposure machine is used in its manufacturing process.
- the colored pattern obtained by the present invention can be significantly finer than 1.5 ⁇ m, in particular 1.0 ⁇ m or less than 2.2 ⁇ m currently commercialized, so that the color filter having the finer colored pattern can be usefully applied to the solid-state imaging device have.
- the present invention provides a solid state image pickup device including the color filter.
- the solid-state imaging device may adopt a configuration known to those skilled in the art, except that the solid-state imaging device is provided with the color filter according to the present invention.
- the photosensitive resin composition obtained a mill base composed of colorant CI Pigment Red 254 28.5%, CI Pigment Yellow 139 9.5%, and polyester dispersant 6.44% based on 100% of the total solids content of the components excluding solvents.
- Binder resin weight average molecular weight 22,000, acid value 80 mgKOH / g, copolymer of methacrylic acid and benzyl methacrylate 25.15%, photopolymerizable compound (dipentaerythritol hexaacrylate (KAYARAD) on the mill base under stirring at DPHA; Nippon Kayaku Co., Ltd.) 12.58% and pentaerythritol triacrylate (manufactured by Miwon Corporation) 12.58%, 1-hydroxycyclohexylphenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical) as a photoinitiator, 5%, A solvent of propylene glycol methyl ether acetate was added
- Example 3 except that the photoinitiator of Example 3 to 2-benzyl-1-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical) It carried out similarly to the obtained photosensitive resin composition.
- the colored photosensitive composition obtained in Examples 1 to 5 After applying the colored photosensitive composition obtained in Examples 1 to 5 by spin coating on a surface of a 4 inch size Si-wafer in a clean room at 23 ° C., it was dried at 90 ° C. for 90 seconds to volatilize the volatile component. A colored photosensitive composition layer was formed. After cooling to 23 ° C., the formed colored photosensitive composition layer was exposed to light using a KrF scanner exposure machine (248 nm). As the photomask, a photomask (mask size of 1.5 um) for forming color pixels in the form of dots was used.
- the developer aqueous solution containing 0.2 parts by weight of tetramethylammonium hydroxide
- the developer was developed for 60 seconds using a puddle at 23 ° C., washed with pure water, and then heated at 220 ° C. for 180 seconds to form a colored pixel.
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- FIG. 1 shows the results of Example 1
- FIG. 2 shows Example 2
- FIG. 3 shows Example 3
- FIG. 4 shows Example 4
- each of the colored patterns has a fine pattern and a square excellent pattern with little LER (line edge roughness) and almost no residual residue scum and no top loss of the pattern.
- the exposure amount of 200 mJ / cm ⁇ 2> or more is required.
- the photosensitive resin composition is a colorant based on 100% of the total solids of the components excluding the solvent.
- Pigment Green 36 23.8% and C.I. Pigment Yellow 139 10.2% and obtained a mill base consisting of 5.14% polyester dispersant, and then binder resin (weight average molecular weight 30,000, acid value 70mgKOH / g, methacrylic acid and benzyl) to the millbase under stirring at 23 °C Copolymer of methacrylate) 35.55%, photopolymerizable compound (Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)) and pentaerythritol triacrylate (made by Miwon Corporation) 5.92%, Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetylox
- the colored photosensitive composition obtained in Examples 6 to 9 After applying the colored photosensitive composition obtained in Examples 6 to 9 by spin coating on a surface of a 4 inch size Si-wafer in a clean room at 23 ° C., it was dried at 90 ° C. for 90 seconds to volatilize the volatile component. A colored photosensitive composition layer was formed. After cooling to 23 ° C., the formed colored photosensitive composition layer was exposed to light using a KrF scanner exposure machine (248 nm). As a photomask, a photomask for forming color pixels in the form of dots was used. It was.
- the developer aqueous solution containing 0.2 parts by weight of tetramethylammonium hydroxide
- the developer was developed for 60 seconds using a puddle at 23 ° C., washed with pure water, and then heated at 220 ° C. for 180 seconds to form a colored pixel.
- the exposure pattern (Eop-Energy of Optimization) when the actual size of the pattern is 1.5 ⁇ m is measured by scanning electron microscopy (SEM) of the mask size of 1.5 ⁇ m.
- SEM scanning electron microscopy
- the colored photosensitive resin composition of Examples 6 to 9 using the oxime ester-based photoinitiator as the photoinitiator can be reduced in high cross-linking time and exposure amount even with a small amount have.
- the micronized pattern can be obtained even at a wavelength of 300 nm or less, but the alignment of each pixel may be slightly disturbed from 1.3 um based on the 1.4 um pixel size.
- the colored photosensitive resin composition obtained a mill base composed of colorant CI Pigment Red 254 28.5%, CI Pigment Yellow 139 9.5%, and polyester dispersant 6.44% based on 100% of the total solids of the components excluding solvents.
- Binder resin copolymer of methacrylic acid with benzyl methacrylate having a weight average molecular weight of 20,000 and an acid value of 120 mgKOH / g
- a photopolymerizable compound dipentaerythritol pentaacrylate
- TOAGOSEI dipentaerythritol pentaacrylate
- pentaerythritol triacrylate manufactured by Miwon Corporation
- the photoinitiator was replaced with 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5 instead of 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical)
- a colored photosensitive resin composition was obtained in the same manner as in Example 10 except that 2% of -triazine (TAZ-TMS; manufactured by Midori kagaku) was added.
- the colored photosensitive composition obtained in Examples 10 and 11 After applying the colored photosensitive composition obtained in Examples 10 and 11 by spin coating on a surface of a 4 inch size Si-wafer in a clean room at 23 ° C., it was dried at 90 ° C. for 90 seconds to volatilize the volatile components. A colored photosensitive composition layer was formed. After cooling to 23 ° C., the formed colored photosensitive composition layer was exposed to light using a KrF scanner exposure machine (248 nm). As the photomask, a photomask for forming color pixels in the form of dots was used.
- the developer aqueous solution containing 0.2 parts by weight of tetramethylammonium hydroxide
- the developer was developed for 60 seconds using a puddle at 23 ° C., washed with pure water, and then heated at 220 ° C. for 180 seconds to form a colored pixel.
- each of the coloring patterns has little fine pattern and LER (line edge roughness) and no residual image. It was possible to form an excellent pattern of square with little physical scum and tops of the pattern, and the optimum exposure amount (Eop) at that time was 90 mJ / cm 2 . In particular, in the case of Example 10 it was possible to implement a good coloring pattern even at 1.0um.
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Abstract
Description
Claims (13)
- 착색제, 바인더수지, 광중합성 화합물, 광중합개시제 및 용매를 포함하는 착색 감광성 수지 조성물에 있어서, 상기 광중합개시제는 300nm 이하에서 반응하는 화합물을 포함하는 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 1에 있어서,상기 광중합개시제는 아세토페논계, 벤조페논계, 티오크산톤계 및 트리아진계 광중합개시제로 이루어진 군으로부터 선택된 적어도 하나이고, 상기 광중합개시제는 착색 감광성 수지 조성물 중의 고형분에 대하여 중량 분율로 5~20중량% 함유되는 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 2에 있어서,상기 광중합개시제는 아세토페논계 및 벤조페논계 광중합개시제로 이루어진 군으로부터 선택된 적어도 하나인 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 1에 있어서,상기 광중합개시제는 옥심에스테르계인 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 4에 있어서,상기 광중합개시제는 착색 감광성 수지 조성물 중의 고형분에 대하여 중량 분율로 1~20중량% 함유되는 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 1에 있어서,상기 광중합개시제는 옥심에스테르계 광중합개시제를 포함하며, 상기 옥심에스테르계 광중합개시제 이외의 다른 광중합개시제를 더 포함하여 이루어진 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 6에 있어서,상기 다른 광중합개시제는 아세토페논계, 벤조페논계, 티오크산톤계, 트리아진계 또는 벤조인계 광중합개시제에서 선택되는 활성라디칼 발생제, 증감제 및 산발생제로 이루어진 군으로부터 선택되는 적어도 하나인 것을 특징으로 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 6에 있어서,상기 옥심에스테르계 광중합개시제는 그를 포함하는 광중합개시제 전체 량에 대하여 중량 분율로 1~99중량% 포함되는 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 6에 있어서,상기 광중합개시제는 착색 감광성 수지 조성물 중의 고형분에 대하여 중량 분율로 1~50중량% 함유되는 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 1에 있어서,상기 300nm 이하의 초단파장 노광기는 KrF 스캐너 노광기(248nm)인 것을 특징으로 하는 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물.
- 청구항 1 내지 10 중 어느 한 항의 착색 감광성 수지 조성물을 기판상에 코팅한 후 300nm 이하의 초단파장 노광기를 사용하여 소정의 패턴으로 노광 및 현상하여서 된 착색 패턴을 포함하는 것을 특징으로 하는 컬러 필터.
- 청구항 11에 있어서,상기 노광기는 KrF 스캐너 노광기((248nm)인 것을 특징으로 하는 컬러필터.
- 청구항 11의 컬러 필터를 포함하는 것을 특징으로 하는 고체 촬상 소자.
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CN2010800384478A CN102770809A (zh) | 2009-07-02 | 2010-07-01 | 用于制备利用300nm以下超短波长曝光器的固体摄像元件的彩色滤光片的着色感光性树脂组合物、利用其的彩色滤光片以及含有该彩色滤光片的固体摄像元件 |
US13/381,289 US8902522B2 (en) | 2009-07-02 | 2010-07-01 | Colored photosensitive resin composition for preparation of color filter of solid-state image sensing device using 300 nm or less ultrashort wave exposure equipment, color filter using same, and solid-state image sensing device containing same |
JP2012517414A JP2012532334A (ja) | 2009-07-02 | 2010-07-01 | 300nm以下の超短波長露光器を利用した固体撮像素子のカラーフィルター製造用着色感光性樹脂組成物、これを利用したカラーフィルターおよびこれを含む固体撮像素子 |
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KR1020090060147A KR20110002606A (ko) | 2009-07-02 | 2009-07-02 | 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 고체 촬상 소자 |
KR10-2009-0060148 | 2009-07-02 | ||
KR10-2009-0060147 | 2009-07-02 | ||
KR1020090060149A KR20110002608A (ko) | 2009-07-02 | 2009-07-02 | 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 고체 촬상 소자 |
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KR1020090060148A KR20110002607A (ko) | 2009-07-02 | 2009-07-02 | 300nm 이하의 초단파장 노광기를 이용한 고체 촬상 소자의 컬러 필터 제조용 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 고체 촬상 소자 |
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JP5757925B2 (ja) * | 2011-08-31 | 2015-08-05 | 富士フイルム株式会社 | 着色組成物、並びに、これを用いたカラーフィルタの製造方法、カラーフィルタ、及び、固体撮像素子 |
JP6155772B2 (ja) * | 2013-04-02 | 2017-07-05 | 東洋インキScホールディングス株式会社 | 感光性着色組成物、着色膜及びカラーフィルタ |
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JP6233271B2 (ja) * | 2013-12-27 | 2017-11-22 | Jsr株式会社 | 感光性樹脂組成物およびレジストパターンの製造方法 |
JP6392549B2 (ja) * | 2014-05-28 | 2018-09-19 | 株式会社タムラ製作所 | アルカリ可溶性樹脂組成物及びアルカリ可溶性樹脂組成物の硬化膜を有するプリント配線板 |
US20170176856A1 (en) | 2015-12-21 | 2017-06-22 | Az Electronic Materials (Luxembourg) S.A.R.L. | Negative-working photoresist compositions for laser ablation and use thereof |
KR102143261B1 (ko) * | 2016-04-01 | 2020-08-10 | 주식회사 엘지화학 | 잉크 조성물, 이로 제조된 경화 패턴, 이를 포함하는 발열체 및 이의 제조방법 |
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KR102374880B1 (ko) | 2017-09-29 | 2022-03-16 | 후지필름 가부시키가이샤 | 착색 감광성 조성물 및 광학 필터의 제조 방법 |
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WO2019159950A1 (ja) | 2018-02-16 | 2019-08-22 | 富士フイルム株式会社 | 感光性組成物 |
TWI787455B (zh) | 2018-02-16 | 2022-12-21 | 日商富士軟片股份有限公司 | 感光性組成物 |
TW201936648A (zh) * | 2018-02-28 | 2019-09-16 | 日商富士軟片股份有限公司 | 感光性組成物 |
KR102435745B1 (ko) | 2018-03-05 | 2022-08-24 | 후지필름 가부시키가이샤 | 감광성 조성물 |
WO2019188653A1 (ja) | 2018-03-26 | 2019-10-03 | 富士フイルム株式会社 | 感光性組成物 |
KR20200122356A (ko) | 2018-03-26 | 2020-10-27 | 후지필름 가부시키가이샤 | 감광성 조성물 |
WO2019202908A1 (ja) * | 2018-04-19 | 2019-10-24 | 富士フイルム株式会社 | パターンの製造方法、光学フィルタの製造方法、固体撮像素子の製造方法、画像表示装置の製造方法、光硬化性組成物および膜 |
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