WO2024058334A1 - Photosensitive resin composition, photosensitive resin film manufactured using same, and color filter - Google Patents

Photosensitive resin composition, photosensitive resin film manufactured using same, and color filter Download PDF

Info

Publication number
WO2024058334A1
WO2024058334A1 PCT/KR2023/005392 KR2023005392W WO2024058334A1 WO 2024058334 A1 WO2024058334 A1 WO 2024058334A1 KR 2023005392 W KR2023005392 W KR 2023005392W WO 2024058334 A1 WO2024058334 A1 WO 2024058334A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
weight
photosensitive resin
resin composition
paragraph
Prior art date
Application number
PCT/KR2023/005392
Other languages
French (fr)
Korean (ko)
Inventor
서광원
박백성
이상호
기승범
김사비나
김광섭
유정호
김지홍
김이주
김익진
조명호
Original Assignee
삼성에스디아이 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Publication of WO2024058334A1 publication Critical patent/WO2024058334A1/en

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14643—Photodiode arrays; MOS imagers
    • H01L27/14645—Colour imagers

Definitions

  • This description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a color filter.
  • An image sensor is a semiconductor that converts photons into electrons and allows them to be displayed on a display or stored in a storage device.
  • the image sensor is classified into a charge coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor, depending on the manufacturing process and application method.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • the image sensor includes a color filter including filter segments of additive primary colors of red, green, and blue. External light that passes through this color filter is converted into color image data (R, G, B data) and driven to the display device through the process of processing it as a signal.
  • the color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and serves to decompose transmitted light into three primary colors. Recently, in order to increase the color uniformity of the color filter, pattern uniformity has been emphasized.
  • One embodiment is to provide a photosensitive resin composition that can suppress diagonal defects and foreign substances while forming a uniform color and thickness of the photosensitive resin film.
  • Another embodiment is to provide a photosensitive resin film manufactured using the photosensitive resin composition.
  • Another embodiment is to provide a color filter manufactured using the photosensitive resin film.
  • One embodiment includes (A) a photopolymerizable compound; (B) photopolymerization initiator; (C) colorant; (D) binder resin; and (E) a solvent, wherein the solvent includes a first solvent to a third solvent, the first solvent has a flash point of less than 40°C, the second solvent has a flash point of 40°C or more to less than 60°C, and 3 The solvent may have a flash point of 60°C or higher.
  • the first solvent, the second solvent, and the third solvent may satisfy Equation 1 below:
  • Equation 1 M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.
  • the first solvent is contained in an amount of 40 parts by weight or more and 80 parts by weight or less
  • the second solvent is contained in an amount of 1 part by weight or more and 50 parts by weight or less
  • the third solvent It may be included in an amount of 0.1 parts by weight or more and 40 parts by weight or less.
  • the first solvent may have a boiling point of 110°C or more and less than 140°C under 1 atm.
  • the first solvent may be an acetate first solvent or an alcohol-based first solvent.
  • the first solvent may be n-butyl acetate (n-BA).
  • the first solvent may be included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
  • the second solvent may have a boiling point of 125°C or more and less than 150°C under 1 atm.
  • the second solvent may be an acetate-based second solvent.
  • the second solvent may be propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate (EGMEA), or a combination thereof.
  • PGMEA propylene glycol monomethyl ether acetate
  • EGMEA ethylene glycol monomethyl ether acetate
  • the second solvent may be included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
  • the third solvent may have a boiling point of 150° C. or higher at 1 atm.
  • the third solvent may have a structure containing two or more ether groups.
  • the third solvent may be diethylene glycol methyl ethyl ether (MEDG).
  • EMG diethylene glycol methyl ethyl ether
  • the third solvent may be included in an amount of 0.1% by weight or more and 25% by weight or less based on 100% by weight of the photosensitive resin composition.
  • the colorant includes a pigment, and the pigment may include a blue pigment, a purple pigment, or a mixture thereof.
  • the photosensitive resin composition includes 0.1% to 20% by weight of the (A) photopolymerizable compound, based on the total amount of the photosensitive resin composition; (B) 0.1% to 5% by weight of photopolymerization initiator; 5% to 50% by weight of the (C) colorant; 0.1% to 20% by weight of the (D) binder resin; And it may include the remaining amount of the solvent (E).
  • Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.
  • Another embodiment provides a color filter including the photosensitive resin film.
  • Another implementation provides a CMOS image sensor including the color filter.
  • the photosensitive resin composition of one embodiment includes three types of solvents with different flash points, thereby forming a uniform color and thickness of the photosensitive resin film while suppressing diagonal defects and foreign matter.
  • substitution means that at least one hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, or already.
  • heterocycloalkyl group refers to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl group, respectively. It means that at least one hetero atom of N, O, S or P is present in the ring compound of ren.
  • (meth)acrylate means that both “acrylate” and “methacrylate” are possible.
  • One embodiment includes (A) a photopolymerizable compound; (B) photopolymerization initiator; (C) colorant; (D) binder resin; and (E) a solvent, wherein the solvent includes a first solvent to a third solvent, the first solvent has a flash point of less than 40°C, the second solvent has a flash point of 40°C or more to less than 60°C, and 3 The solvent provides a photosensitive resin composition having a flash point of 60° C. or higher.
  • flash point of a volatile substance means the lowest temperature at which a flammable substance can be created and ignited in the air.
  • the flash point of volatile substances here, each solvent
  • 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 begins to boil, and changes depending on the external pressure.
  • One embodiment above addresses the boiling point under 1 atm.
  • volatilization refers to the phenomenon in which a liquid turns into a gas at room temperature and flies away
  • volatility refers to such a property
  • color filters for CMOS IMAGE SENSOR are composed of three colors: red, green, and blue.
  • a photosensitive resin composition containing a colorant of a specific color is coated, soft-baked, exposed, developed, and hard-baked on a substrate or a patterned photosensitive resin film thereon.
  • a color filter can be completed by forming a film and repeating this series of processes for each color of the colorant.
  • the order of formation of the photosensitive resin film is green ⁇ blue ⁇ red; Or the general order is green ⁇ red ⁇ blue.
  • the coating is generally performed using a spin coating method, but this method causes several problems. Specifically, thickness uniformity may be low due to limitations in the coating method, or light scattering, color unevenness, and diagonal defects may appear due to the influence of the pattern of the lower photosensitive resin film. In particular, since the color filter for CIS is implemented as a thin film, if foreign substances are mixed during the coating process, defects may occur and the yield of the product may decrease.
  • the higher the volatility of the solvent in the photosensitive resin composition the faster the drying speed during the coating process.
  • the volatility of the solvent is too high and volatilization occurs not only on the coating surface but also on the lower part, color unevenness, thickness unevenness, etc. may appear in the resulting photosensitive resin film.
  • the lower the volatility of the solvent in the photosensitive resin composition the slower the drying speed may be during the coating process, and if the colorant particles become uneven or foreign substances are incorporated during the long-term drying process, the diagonal lines in the resulting photosensitive resin film may appear. Defects, foreign substances, etc. may appear.
  • the above embodiment is intended to provide a photosensitive resin composition that can suppress diagonal defects and foreign substances while uniformly forming the color and thickness of the photosensitive resin film.
  • the higher the flash point of a substance the higher its boiling point and the lower its volatility. Since the photosensitive resin composition of the above embodiment includes three types of solvents with different flash points, the volatilization rate and volatilization position of the solvents can be controlled harmoniously.
  • the photosensitive resin composition of one embodiment has uniform color and thickness while suppressing diagonal defects and foreign matter by using a solvent containing at least one each of the first solvent, the second solvent, and the third solvent.
  • a resin film can be formed.
  • the first solvent with the lowest flash point and highest volatility is the main solvent and has the highest content
  • the second and third solvents are auxiliary solvents, which are the first solvent.
  • the content may be less compared to the solvent.
  • the first solvent, the second solvent, and the third solvent may satisfy Equation 1 below:
  • Equation 1 M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.
  • the content of the third solvent with the highest flash point and lowest volatility is the lowest
  • the content of the first solvent with the lowest flash point and highest volatility is higher than the content of the third solvent
  • the content of the third solvent with the lowest flash point and volatility is intermediate. 2
  • the content of the solvent may be similar to or less than the content of the first solvent.
  • the first solvent is 40 parts by weight or more and 80 parts by weight or less, 50 parts by weight or more and 80 parts by weight or less, or 55 parts by weight or more and 80 parts by weight or less. Included;
  • the second solvent is included in an amount of 1 part by weight or more and 50 parts by weight or less, 5 parts by weight or more and 40 parts by weight or less, or 10 parts by weight or more and 30 parts by weight or less;
  • the third solvent may be included in an amount of 0.1 part by weight or more and 40 parts by weight or less, or 1 part by weight or more and 30 parts by weight or less.
  • the closer the content of the first solvent is to 55 parts by weight or more to 80 parts by weight or less;
  • the closer the content of the second solvent is to 10 parts by weight or more to 30 parts by weight or less;
  • the closer the third solvent is to 1 part by weight or more to 10 parts by weight or less, the better the synergy effect of the first to third solvents.
  • the total amount of the first to third solvents may be 5% to 70% by weight, for example, 40% to 50% by weight of the photosensitive resin composition.
  • the photosensitive resin composition has excellent applicability and a coating film with excellent flatness can be obtained.
  • the first solvent may have a flash point of less than 40°C, 20°C or higher to 35°C or lower, or 25°C or higher to 35°C or lower. Additionally, the first solvent may have a boiling point of 114°C or higher to 138°C, 118°C or higher to 134°C or lower, or 122°C or higher to 130°C or lower at 1 atm.
  • the first solvent having the flash point and boiling point may be an acetate-based first solvent or an alcohol-based first solvent.
  • the first solvent is an acetate-based first solvent and may be n-butyl acetate (n-BA).
  • the first solvent may be included in 1% by weight to 50% by weight, 4% by weight to 40% by weight, or 25% by weight to 40% by weight based on 100% by weight of the photosensitive resin composition.
  • the second solvent may have a flash point of 40°C or higher to less than 60°C, 40°C or higher to 55°C or lower, or 40°C or higher to 50°C or lower. Additionally, the second solvent may have a boiling point of 125°C to 150°C, 130°C to 149°C, or 140°C to 148°C at 1 atm.
  • the second solvent having the flash point and boiling point may be an acetate-based second solvent.
  • the second solvent is an acetate-based second solvent, such as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate (EGMEA), or a combination thereof. It can be.
  • the second solvent may be included in 1% by weight to 50% by weight, 4% by weight to 40% by weight, or 4% by weight to 15% by weight based on 100% by weight of the photosensitive resin composition.
  • the third solvent may have a flash point of 65°C or higher, 65°C or higher to 89°C or lower, or 65°C or higher to 85°C or lower. Additionally, the third solvent may have a boiling point of 150°C or higher, 160°C or higher to 190°C or lower, or 170°C or higher to 180°C or lower at 1 atm.
  • the third solvent having the flash point and boiling point may have a structure containing two or more ether groups.
  • the third solvent may be diethylene glycol methyl ethyl ether (MEDG).
  • the third solvent may be included in 0.1% by weight to 25% by weight, 0.1% by weight to 20% by weight, or 0.4% by weight to 15% by weight based on 100% by weight of the photosensitive resin composition.
  • the photopolymerizable compound may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.
  • the photopolymerizable compound By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern with excellent heat resistance, light resistance, and chemical resistance by sufficiently polymerizing the compound upon exposure to light in the pattern formation process.
  • photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di.
  • Examples of commercially available photopolymerizable compounds are as follows.
  • Examples of the monofunctional ester of (meth)acrylic acid include Aronix M- 101® , M- 111® , and M- 114® manufactured by Toagosei Chemical Co., Ltd.; Nippon Kayaku Co., Ltd.'s KAYARAD TC-110S ® , KAYARAD TC-120S ® , etc.; Examples include V-158 ® and V-2311 ® manufactured by Osaka Yuki Chemical Co., Ltd.
  • Examples of the above-mentioned difunctional ester of (meth)acrylic acid include Aronics M-210 ® , M-240 ® , and M-6200 ® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ® , HX-220 ® , R-604 ® , etc.; Examples include V-260 ® , V-312 ® , and V-335 HP ® manufactured by Osaka Yuki Chemical Engineering Co., Ltd.
  • Examples of the trifunctional ester of (meth)acrylic acid include Aronics M-309 ® , M-400 ® , M-405 ® , M-450 ® , and M manufactured by Toagosei Chemical Co., Ltd. -710 ® , M-8030 ® , M-8060 ® , etc.; Nippon Kayaku Co., Ltd.'s KAYARAD TMPTA ® , DPCA-20 ® , Dong-30 ® , Dong-60 ® , Dong-120 ® , etc.; Examples include V-295 ® , Dong-300 ® , Dong-360 ® , Dong-GPT ® , Dong-3PA ® , and Dong-400 ® manufactured by Osaka Yuki Kayaku Kogyo Co., Ltd.
  • the above products can be used alone or in combination of two or more types.
  • the photopolymerizable compound may be used by treating it with an acid anhydride to provide better developability.
  • the photopolymerizable compound may be included in an amount of 0.1% to 20% by weight, specifically 1% to 15% by weight, for example, 2% to 13% by weight, based on the total amount of the photosensitive resin composition.
  • the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.
  • the photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, 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. You can use it.
  • acetophenone-based compounds examples include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.
  • benzophenone-based compounds examples include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.
  • thioxanthone-based compounds examples include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.
  • benzoin-based compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.
  • triazine-based compounds examples 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, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-
  • Examples of the oxime-based compounds include O-acyloxime-based 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, O-ethoxycarbonyl- ⁇ -oxyamino-1-phenylpropan-1-one etc. can be used.
  • O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime-O- Acetate, etc. can be mentioned.
  • the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and fluorene-based compounds.
  • the photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.
  • photosensitizer examples include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.
  • the photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, specifically 0.3% by weight to 4.5% by weight, for example, 0.5% by weight to 4% by weight, based on the total amount of the photosensitive resin composition.
  • the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure during the pattern formation process to obtain excellent reliability, the heat resistance, light resistance, and chemical resistance of the pattern are excellent, resolution and adhesion are also excellent, and there is no damage from unreacted initiators. Deterioration of transmittance can be prevented.
  • the colorant may include a pigment, and in this case, the resin composition of one embodiment may be a pigment-type composition.
  • the pigment green pigment, blue pigment, red pigment, purple pigment, yellow pigment, black pigment, etc. can be used.
  • the red pigment is classified as C.I. in the color index.
  • Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89, etc. can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
  • the purple pigment is C.I. within the Color Index. Violet Pigment 23 (V.23), C.I. Violet Pigment 29, Dioxazine Violet, First Violet B, Methyl Violet Lake, Indanthrene Brilliant Violet, etc. can be used, and these can be used alone or in a mixture of two or more, but are not necessarily limited thereto.
  • the green pigment is classified as C.I. in the color index. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green pigment 59, etc. can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
  • the blue pigment is C.I. in the color index.
  • Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Blue pigment 15:6, C.I. Copper phthalocyanine pigments such as blue pigment 16 can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
  • the yellow pigment is classified as C.I. in the color index.
  • Yellow Pigment 185 C.I. Isoindoline pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. Nickel complex pigments such as yellow pigment 150 can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
  • the black pigment may include aniline black, perylene black, titanium black, and carbon black within the color index, and may be used alone or in a mixture of two or more types, but is not necessarily limited thereto.
  • the above pigments can be used alone or in a mixture of two or more.
  • the pigment may be a blue pigment, a purple pigment, or a mixture thereof.
  • the pigment may be included in the photosensitive resin composition for a color filter in the form of a dispersion.
  • This pigment dispersion may be composed of the pigment, solvent, dispersant, dispersion resin, etc.
  • the solid pigment may be included in an amount of 5% to 20% by weight, for example, 8% to 15% by weight, based on the total amount of the pigment dispersion.
  • the solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc.
  • propylene glycol methyl ether acetate is preferred. You can.
  • the dispersant helps the pigment to be uniformly dispersed in the dispersion, and nonionic, anionic, or cationic dispersants can be used.
  • nonionic, anionic, or cationic dispersants can be used.
  • Water, alkyl amine, etc. can be used, and these can be used alone or in a mixture of two or more types.
  • the dispersion resin may be an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patterning of the pixel.
  • the colorant may include the pigment and may further include a dye, and in this case, the resin composition of the embodiment may be a hybrid composition. Additionally, the dye is not particularly limited, but may include a metal complex dye.
  • the metal complex dye can be a compound having a maximum absorbance in the wavelength range of 200 nm to 650 nm.
  • a metal complex dye of any color soluble in an organic solvent can be used as long as it has an absorbance in the above range. You can use it.
  • the metal complex dye includes a green dye with maximum absorbance in the 530 nm to 680 nm wavelength range, a yellow dye with maximum absorbance in the 200 nm to 400 nm wavelength range, and a maximum absorbance in the 300 nm to 500 nm wavelength range.
  • An orange dye with a maximum absorbance in the wavelength range of 500 nm to 650 nm, a red dye with a maximum absorbance, or a combination thereof can be used.
  • the above metal complex dyes include direct dyes, acidic dyes, basic dyes, acid mordant dyes, sulfuric dyes, reduced dyes, azoic dyes, disperse dyes, reactive dyes, oxidizing dyes, oil-soluble dyes, azo dyes, anthraquinone dyes, and indigoid dyes. , carbonium ion dye, phthalocyanine dye, nitro dye, quinoline dye, cyanine dye, polymethine dye, or a combination thereof can be used.
  • the metal complex dye may include at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.
  • the metal complex dye is C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent, dye; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C.I.s such as 104, 105, 106, 109, etc. acid dye; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct dye, C.I. C.I. such as Basic, Green 1, etc. Basic dye;C.I. C.I.
  • the dye containing the metal complex may have a solubility in a solvent used in the photosensitive resin composition according to one embodiment, that is, a solvent described later, of 5 or more, specifically 5 to 10.
  • the solubility can be obtained by the amount (g) of the dye dissolved in 100 g of the solvent.
  • the solvent is, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone. (cyclohexanone), 3-methoxy-1-butanol (3-methoxy-1-butanol), or a combination thereof can be used.
  • PGMEA propylene glycol monomethyl ether acetate
  • EL ethyl lactate
  • ESA ethylene glycol ethyl acetate
  • cyclohexanone cyclohexanone
  • 3-methoxy-1-butanol 3-methoxy-1-butanol
  • the dye containing the metal complex may be included in an amount of 0.01% by weight to 1% by weight, for example, 0.01% by weight to 0.5% by weight, based on the total amount of the photosensitive resin composition.
  • the dye containing the metal complex is used in the above range, high luminance and contrast ratio can be achieved at the desired color coordinate.
  • the dye and the pigment When the dye and the pigment are mixed and used, they can be mixed at a weight ratio of 0.1:99.9 to 99.9:0.1, specifically 1:9 to 9:1.
  • chemical resistance and maximum absorption wavelength When mixed in the above weight ratio range, chemical resistance and maximum absorption wavelength can be controlled to an appropriate range, and high luminance and contrast ratio can be expressed at the desired color coordinate.
  • the colorant may be included in an amount of 5% to 50% by weight, specifically 6% to 40% by weight, for example, 7% to 30% by weight, based on the total amount of the photosensitive resin composition.
  • the colorant is included within the above range, the coloring effect and developability are excellent.
  • the binder resin may include an acrylic resin.
  • the acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.
  • the first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
  • the first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, based on the total amount of the acrylic binder resin.
  • the second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, and vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, Unsaturated carboxylic acid ester compounds such as 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; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycid
  • acrylic resin examples include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Examples include, but are not limited to, late copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and these may be used alone or in combination of two or more types. .
  • the binder resin may include an epoxy-based binder resin.
  • the binder resin can improve heat resistance by further including an epoxy-based binder resin.
  • the epoxy-based binder resin may include, for example, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, cycloaliphatic epoxy resin, or a combination thereof, but is limited thereto. That is not the case.
  • the binder resin containing the epoxy-based binder resin ensures the dispersion stability of colorants such as pigments, which will be described later, and helps form pixels with a desired resolution during the development process.
  • the epoxy-based binder resin may be included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, based on the total amount of the binder resin.
  • the epoxy-based binder resin is included in the above range, the remaining film rate and chemical resistance can be greatly improved.
  • the epoxy equivalent weight of the epoxy-based binder resin may be 150 g/eq to 200 g/eq.
  • an epoxy-based binder resin having an epoxy equivalent weight within the above range is included in the binder resin, there is an advantageous effect in improving the curability of the formed pattern and fixing the colorant in the structure in which the pattern is formed.
  • the binder resin may be dissolved in a solvent described later in solid form to form a photosensitive resin composition.
  • the binder resin in the solid form may be about 0.1% by weight to 30% by weight, for example, 20% by weight to 30% by weight, based on the total amount of the binder resin solution dissolved in the solvent.
  • the binder resin may be included in an amount of 0.1% to 20% by weight, specifically 0.5% to 15% by weight, for example, 1% to 10% by weight, based on the total amount of the photosensitive resin composition.
  • the binder resin When the binder resin is contained within the above range, developability is excellent when manufacturing a color filter, crosslinking is improved, and excellent surface smoothness can be obtained.
  • the photosensitive resin composition contains malonic acid to prevent stains or spots upon application, to improve leveling performance, and to prevent the creation of residues due to non-development; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Surfactants; and at least one additive selected from radical polymerization initiators.
  • the additives can be easily adjusted according to desired physical properties.
  • the coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, ⁇ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, ⁇ Examples include isocyanate propyl triethoxysilane, ⁇ glycidoxy propyl trimethoxysilane, and ⁇ epoxycyclohexyl)ethyltrimethoxysilane, and these can be used alone or in a mixture of two or more types.
  • the silane-based coupling agent may be specifically used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.
  • the photosensitive resin composition for a color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary.
  • a surfactant such as a fluorine-based surfactant
  • fluorine-based surfactant examples include DIC's F-482, F-484, and F-478, but are not limited thereto.
  • the surfactant is preferably contained in an amount of 0.01 wt% to 5 wt%, and more preferably in an amount of 0.01 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If it is outside the above range, it is undesirable because it may cause problems with foreign substances occurring after development.
  • antioxidants and stabilizers may be added to the photosensitive resin composition within the range that does not impair the physical properties.
  • a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.
  • a color filter manufactured using the above-described photosensitive resin composition is provided.
  • the manufacturing method of the color filter is as follows.
  • the photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.1 ⁇ m to 10 ⁇ m, using an appropriate method such as spin coating, roller coating, or spray coating, on a glass substrate.
  • light is irradiated to the substrate on which the photosensitive resin composition layer is formed to form a pattern necessary for a color filter.
  • a light source used for irradiation UV, electron beams, or The above irradiation process can also be performed by further using a photoresist mask.
  • the photosensitive resin composition layer irradiated with the light source is treated with a developer.
  • the non-exposed portion of the photosensitive resin composition layer is dissolved, thereby forming a pattern required for the color filter.
  • crack resistance, solvent resistance, etc. can be improved by heating the image pattern obtained through development in the above process again or curing it by irradiation with actinic rays.
  • CMOS image sensor including the color filter is provided.
  • the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, then a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 60 minutes. Next, dye and pigment dispersion as a colorant were added and stirred at room temperature for 30 minutes. Additives were added here, stirred at room temperature for 1 hour, and filtered three times to remove impurities, thereby preparing a photosensitive resin composition.
  • Example 8 (A) Photopolymerization compound A-1 100 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 (B) Light curing initiator B-1 100 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (C) coloring agent C-1 18 31.5 31.5 31.5 31.5 31.5 31.5 31.5 C-2 18 13.3 13.3 13.3 13.3 13.3 13.3 13.3 13.3 (D) bookbinder profit D-1 30 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 (E) menstruum E-1 - 4.8 9.6 14.4 19.2 24 28.8 33.6 38.4 E-2 - 38.4 33.6 28.8 24 19.2 14.4 9.6 4.8 E-3 - 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 E-4 - - - - - - - - - E-5 - - - - - -
  • Example 14 (A) Photopolymerization compound A-1 100 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 (B) Light curing initiator B-1 100 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (C) coloring agent C-1 18 31.5 31.5 31.5 31.5 31.5 31.5 C-2 18 13.3 13.3 13.3 13.3 13.3 13.3 (D) bookbinder profit D-1 30 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 (E) menstruum E-1 - 33.12 31.2 28.8 26.4 24 21.6 19.2 E-2 - 14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.4 E-3 - 0.48 2.4 4.8 7.2 9.6 12 14.4 E-4 - - - - - - - - E-5 - - - - - - - - E-6 - - - - - - - - - - - -
  • (D-1) Acrylic binder resin with an acid value of 30 to 180 KOHmg/g and a weight average molecular weight of 5000 to 20000 g/mol (RY-100, manufacturer: Showa Denko)
  • the flash point of each solvent can be measured using a tag-sealed equipment (Anton Paar TAG4) according to the ASTM D56 test method.
  • Color filter specimens including a patterned photosensitive resin film were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the color uniformity of the photosensitive resin film was evaluated.
  • Color filter specimens containing a photosensitive resin film were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the thickness uniformity of the photosensitive resin film was evaluated.
  • Color filter specimens including photosensitive resin films were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the diagonal defects of the photosensitive resin films were evaluated.
  • Color filter specimens including photosensitive resin films were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the area of foreign matter in the patterned photosensitive resin film was evaluated.
  • Example 1 Weight ratio of solvent in photosensitive resin composition Evaluation of color filter specimens E-1 E-2 E-3 E-4 E-5 E-6 Color uniformity (ea) Thickness Uniformity ( ⁇ ) Bad diagonal line Foreign matter area (sq%)
  • Example 1 80 10 - - - 1285 31 O 2.8
  • Example 2 20 70 10 - - - 1281 29 O 2.7
  • Example 3 30
  • Example 3 30
  • Example 4 40
  • Example 4 40 50 10 - - - 1267 28 O 2.6
  • Example 5 50
  • Example 6 60 30 10 - - - 1153 24 O 2.1
  • Example 7 70 20 10 - - - 1150 23 O 2.0
  • Example 8 80 10 10 - - - 1148 22 O 1.8
  • Example 9 69 30 One - - - 1147 22 O 1.8
  • Example 10 65 30 5 - - - 1151 23 O 2.0
  • Example 6 60
  • Example 11 55
  • Example 12 50
  • Example 13 45
  • Example 14 40
  • the color filter specimens manufactured using each of the photosensitive resin compositions of Examples 1 to 14 had uniform color and thickness of the photosensitive resin film while suppressing diagonal defects and foreign matter.
  • the photosensitive resin The color and thickness of the film are not uniform, or diagonal defects and foreign matter occur.
  • the color and thickness of the photosensitive resin film is not uniform, or diagonal defects and foreign substances occur.
  • the content of the first to third solvents satisfies Equation 1 below;
  • the closer the content of the first solvent is to 55 parts by weight or more to 80 parts by weight or less;
  • the closer the content of the second solvent is to 10 parts by weight or more to 30 parts by weight or less;
  • the synergy effect of the first to third solvents may be improved as the amount of the third solvent increases from 1 part by weight to 30 parts by weight.
  • Equation 1 M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Optics & Photonics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film manufactured using same, and a color filter. Specifically, provided in one implementation is a photosensitive resin composition comprising: (A) a photopolymerizable compound; (B) a photopolymerizable initiator; (C) a coloring agent; (D) binder resin; and (E) a solvent, wherein the solvent includes a first solvent to a third solvent, the first solvent having a flash point higher than 40 ℃, the second solvent having a flash point of 40 ℃ or higher and lower than 60 ℃, and the third solvent having a flash point of 60 ℃ or higher.

Description

감광성 수지 조성물, 이를 이용하여 제조된 감광성 수지막 및 컬러 필터Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same
본 기재는 감광성 수지 조성물, 이를 이용하여 제조된 감광성 수지막 및 컬러 필터에 관한 것이다.This description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a color filter.
이미지 센서는 광자를 전자로 전환하여 디스플레이로 표시하거나 저장 장치에 저장할 수 있게 하는 반도체에 해당된다.An image sensor is a semiconductor that converts photons into electrons and allows them to be displayed on a display or stored in a storage device.
상기 이미지 센서는, 제작 공정과 응용 방식에 따라, 고체 촬상 소자(charge coupled device, CCD) 이미지 센서와 상보성 금속 산화물 반도체(complementary metal oxide semiconductor, CMOS) 이미지 센서로 분류된다.The image sensor is classified into a charge coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor, depending on the manufacturing process and application method.
구체적으로, 상기 이미지 센서는, 적색(red), 녹색(green), 청색(blue)의 덧셈 혼합 원색의 필터 세그먼트(filter segment)를 포함하는 컬러 필터(color filter)를 구비한다. 이러한 컬러 필터를 통과한 외부의 빛은, 컬러 이미지 데이터(R, G, B 데이터)로 변환되고 신호로 처리되는 과정을 통해 디스플레이 장치로 구동된다.Specifically, the image sensor includes a color filter including filter segments of additive primary colors of red, green, and blue. External light that passes through this color filter is converted into color image data (R, G, B data) and driven to the display device through the process of processing it as a signal.
상기 컬러 필터는, 통상 적(R), 녹(G), 및 청(B)의 3원색의 착색 패턴을 구비하고 있어 투과광을 3원색으로 분해하는 역할을 담당하고 있다. 최근에는 상기 컬러 필터의 색 균일도를 높이기 위해, 패턴의 균일성(uniformity)이 강조되고 있다. The color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and serves to decompose transmitted light into three primary colors. Recently, in order to increase the color uniformity of the color filter, pattern uniformity has been emphasized.
다만, 상기 컬러 필터의 패턴 모양 중 딤플(dimple) 패턴이 있는 표면에서는, 광 산란, 색 불균일 등이 심해질 수 있다.However, on the surface of the color filter with a dimple pattern, light scattering and color unevenness may become worse.
일 구현예는 감광성 수지막의 색 및 두께를 균일하게 형성하면서도 사선 불량 및 이물을 억제할 수 있는 감광성 수지 조성물을 제공하기 위한 것이다.One embodiment is to provide a photosensitive resin composition that can suppress diagonal defects and foreign substances while forming a uniform color and thickness of the photosensitive resin film.
다른 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 감광성 수지막을 제공하기 위한 것이다.Another embodiment is to provide a photosensitive resin film manufactured using the photosensitive resin composition.
또 다른 일 구현예는 상기 감광성 수지막을 이용하여 제조된 컬러 필터를 제공하기 위한 것이다.Another embodiment is to provide a color filter manufactured using the photosensitive resin film.
일 구현예는 (A) 광중합성 화합물; (B) 광중합 개시제; (C) 착색제; (D) 바인더 수지; 및 (E) 용매를 포함하고, 상기 용매는 제1 용매 내지 제3 용매를 포함하고, 제1 용매는 인화점이 40 ℃ 미만이고, 제2 용매는 인화점이 40 ℃ 이상 내지 60 ℃ 미만이고, 제3 용매는 인화점이 60 ℃ 이상일 수 있다.One embodiment includes (A) a photopolymerizable compound; (B) photopolymerization initiator; (C) colorant; (D) binder resin; and (E) a solvent, wherein the solvent includes a first solvent to a third solvent, the first solvent has a flash point of less than 40°C, the second solvent has a flash point of 40°C or more to less than 60°C, and 3 The solvent may have a flash point of 60°C or higher.
상기 제1 용매, 상기 제2 용매 및 상기 제3 용매는 하기 수학식 1을 만족할 수 있다:The first solvent, the second solvent, and the third solvent may satisfy Equation 1 below:
[수학식 1][Equation 1]
M1 > (M2+M3)M1 > (M2+M3)
상기 수학식 1에서, M1은 상기 제1 용매의 중량이고, M2는 상기 제2 용매의 중량이고, M3는 상기 제3 용매의 중량이다.In Equation 1, M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.
상기 용매의 총 중량 100 중량부 중에서, 상기 제1 용매는 40 중량부 이상 내지 80 중량부 이하로 포함되고, 상기 제2 용매는 1 중량부 이상 내지 50 중량부 이하로 포함되고, 상기 제3 용매는 0.1 중량부 이상 내지 40 중량부 이하로 포함될 수 있다.Of the total weight of 100 parts by weight of the solvent, the first solvent is contained in an amount of 40 parts by weight or more and 80 parts by weight or less, the second solvent is contained in an amount of 1 part by weight or more and 50 parts by weight or less, and the third solvent It may be included in an amount of 0.1 parts by weight or more and 40 parts by weight or less.
상기 제1 용매는 1 atm 하에서 비점이 110 ℃ 이상 내지 140 ℃ 미만일 수 있다.The first solvent may have a boiling point of 110°C or more and less than 140°C under 1 atm.
상기 제1 용매는 아세테이트 제1 용매 또는 알코올계 제1 용매일 수 있다.The first solvent may be an acetate first solvent or an alcohol-based first solvent.
상기 제1 용매는 n-부틸 아세테이트(n-butyl acetate, n-BA)일 수 있다.The first solvent may be n-butyl acetate (n-BA).
상기 제1 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하로 포함될 수 있다.The first solvent may be included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
상기 제2 용매는 1 atm 하에서 비점이 125 ℃ 이상 내지 150 ℃ 미만일 수 있다.The second solvent may have a boiling point of 125°C or more and less than 150°C under 1 atm.
상기 제2 용매는 아세테이트계 제2 용매일 수 있다.The second solvent may be an acetate-based second solvent.
상기 제2 용매는 프로필렌 글리콜 모노메틸 에테르 아세테이트(propylene glycol monomethyl ether acetate, PGMEA), 에틸렌글리콜 모노 메틸 에테르 아세테이트(Ethylene glycol monomethyl ether acetate, EGMEA), 또는 이들의 조합일 수 있다.The second solvent may be propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate (EGMEA), or a combination thereof.
상기 제2 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하로 포함될 수 있다.The second solvent may be included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
상기 제3 용매는 1 atm 하에서 비점이 150 ℃ 이상일 수 있다.The third solvent may have a boiling point of 150° C. or higher at 1 atm.
상기 제3 용매는 2개 이상의 에테르기를 포함하는 구조를 가질 수 있다.The third solvent may have a structure containing two or more ether groups.
상기 제3 용매는 디에틸렌 글리콜 메틸 에틸 에테르(diethylene glycol methyl ethyl ether, MEDG)일 수 있다.The third solvent may be diethylene glycol methyl ethyl ether (MEDG).
상기 제3 용매는 상기 감광성 수지 조성물 100 중량% 중 0.1 중량% 이상 내지 25 중량% 이하로 포함될 수 있다.The third solvent may be included in an amount of 0.1% by weight or more and 25% by weight or less based on 100% by weight of the photosensitive resin composition.
상기 착색제는 안료를 포함하고, 상기 안료는 청색 안료, 자색 안료 또는 이들의 혼합물을 포함할 수 있다.The colorant includes a pigment, and the pigment may include a blue pigment, a purple pigment, or a mixture thereof.
상기 감광성 수지 조성물은, 상기 감광성 수지 조성물 총량에 대해, 상기 (A) 광중합성 화합물 0.1 중량% 내지 20 중량%; 상기 (B) 광중합 개시제 0.1 중량% 내지 5 중량%; 상기 (C) 착색제 5 중량% 내지 50 중량%; 상기 (D) 바인더 수지 0.1 중량% 내지 20 중량%; 및 상기 (E) 용매 잔부량을 포함할 수 있다.The photosensitive resin composition includes 0.1% to 20% by weight of the (A) photopolymerizable compound, based on the total amount of the photosensitive resin composition; (B) 0.1% to 5% by weight of photopolymerization initiator; 5% to 50% by weight of the (C) colorant; 0.1% to 20% by weight of the (D) binder resin; And it may include the remaining amount of the solvent (E).
다른 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 감광성 수지막을 제공한다.Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.
또 다른 일 구현예는 상기 감광성 수지막을 포함하는 컬러 필터를 제공한다.Another embodiment provides a color filter including the photosensitive resin film.
다른 일 구현예는 상기 컬러 필터를 포함하는 CMOS 이미지 센서를 제공한다.Another implementation provides a CMOS image sensor including the color filter.
기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Details of other aspects of the invention are included in the detailed description below.
일 구현예의 감광성 수지 조성물은, 인화점이 서로 다른 3종의 용매를 포함함으로써, 감광성 수지막의 색 및 두께를 균일하게 형성하면서도 사선 불량 및 이물을 억제할 수 있다.The photosensitive resin composition of one embodiment includes three types of solvents with different flash points, thereby forming a uniform color and thickness of the photosensitive resin film while suppressing diagonal defects and foreign matter.
이하, 본 발명의 구현 예를 상세히 설명하기로 한다. 　다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.Hereinafter, an implementation example of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.
본 명세서에서 특별한 언급이 없는 한, "치환"이란 화합물 중의 적어도 하나의 수소 원자가 할로겐 원자(F, Cl, Br, I), 히드록시기, C1 내지 C20 알콕시기, 니트로기, 시아노기, 아민기, 이미노기, 아지도기, 아미디노기, 히드라지노기, 히드라조노기, 카르보닐기, 카르바밀기, 티올기, 에스테르기, 에테르기, 카르복실기 또는 그것의 염, 술폰산기 또는 그것의 염, 인산이나 그것의 염, C1 내지 C20 알킬기, C2 내지 C20 알케닐기, C2 내지 C20 알키닐기, C6 내지 C30 아릴기, C3 내지 C20 사이클로알킬기, C3 내지 C20 사이클로알케닐기, C3 내지 C20 사이클로알키닐기, C2 내지 C20 헤테로사이클로알킬기, C2 내지 C20 헤테로사이클로알케닐기, C2 내지 C20 헤테로사이클로알키닐기 또는 이들의 조합의 치환기로 치환된 것을 의미한다.Unless otherwise specified herein, “substitution” means that at least one hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, or already. No group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group. , C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, or a combination thereof.
본 명세서에서 특별한 언급이 없는 한, "헤테로사이클로알킬기", "헤테로사이클로알케닐기", "헤테로사이클로알키닐기" 및 "헤테로사이클로알킬렌기"란 각각 사이클로알킬, 사이클로알케닐, 사이클로알키닐 및 사이클로알킬렌의 고리 화합물 내에 적어도 하나의 N, O, S 또는 P의 헤테로 원자가 존재하는 것을 의미한다.Unless otherwise specified herein, “heterocycloalkyl group”, “heterocycloalkenyl group”, “heterocycloalkynyl group”, and “heterocycloalkylene group” refer to cycloalkyl, cycloalkenyl, cycloalkynyl, and cycloalkyl group, respectively. It means that at least one hetero atom of N, O, S or P is present in the ring compound of ren.
본 명세서에서 특별한 언급이 없는 한, "(메타)아크릴레이트"는 "아크릴레이트"와 "메타크릴레이트" 둘 다 가능함을 의미한다.Unless otherwise specified herein, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible.
본 명세서 내 화학식에서 별도의 정의가 없는 한, 화학 결합이 그려져야 하는 위치에 화학결합이 그려져 있지 않은 경우는 상기 위치에 수소 원자가 결합되어 있음을 의미한다.Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.
(감광성 수지 조성물)(Photosensitive resin composition)
일 구현예는 (A) 광중합성 화합물; (B) 광중합 개시제; (C) 착색제; (D) 바인더 수지; 및 (E) 용매를 포함하고, 상기 용매는 제1 용매 내지 제3 용매를 포함하고, 제1 용매는 인화점이 40 ℃ 미만이고, 제2 용매는 인화점이 40 ℃ 이상 내지 60 ℃ 미만이고, 제3 용매는 인화점이 60 ℃ 이상인, 감광성 수지 조성물을 제공한다.One embodiment includes (A) a photopolymerizable compound; (B) photopolymerization initiator; (C) colorant; (D) binder resin; and (E) a solvent, wherein the solvent includes a first solvent to a third solvent, the first solvent has a flash point of less than 40°C, the second solvent has a flash point of 40°C or more to less than 60°C, and 3 The solvent provides a photosensitive resin composition having a flash point of 60° C. or higher.
휘발 물질의　"인화점(引火點)"이란　공기 중에 가연성 물질을 만들어내어 인화할 수 있게 하는 가장 낮은 온도를 의미한다. 휘발 물질(여기서는 상기 각 용매)의 인화점은 ASTM D56 시험법에 따라 태크밀폐식 장비(Anton Paar社 TAG4)를 사용하여 측정할 수 있다.The “flash point” of a volatile substance means the lowest temperature at which a flammable substance can be created and ignited in the air. The flash point of volatile substances (here, each solvent) can be measured using tag-sealed equipment (Anton Paar TAG4) according to the ASTM D56 test method.
한편, 액체 물질의 "비점(沸點)"이란 해당 액체 물질의　증기압이 외부 압력과 같아져 끓기 시작하는 온도이며, 외부의 압력에 따라 변화하게 된다. 상기 일 구현예에서는 1 atm 하에서의 비점을 다룬다. Meanwhile, 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 begins to boil, and changes depending on the external pressure. One embodiment above addresses the boiling point under 1 atm.
또한, "휘발"은 상온에서 액체가 기체로 되어 날아 흩어지는 현상을 의미하며, "휘발성(揮發性)"은 그런 성질을 말한다.In addition, “volatilization” refers to the phenomenon in which a liquid turns into a gas at room temperature and flies away, and “volatility” refers to such a property.
일반적으로 CMOS IMAGE SENSOR용(이하 CIS로 명기) 컬러 필터는 적색(red), 녹색(green), 청색(blue)의 삼색으로 구성되어 있다.In general, color filters for CMOS IMAGE SENSOR (hereinafter referred to as CIS) are composed of three colors: red, green, and blue.
특정 색상의 착색제를 함유하는 감광성 수지 조성물을 기판 또는 그 위의 패턴화된 감광성 수지막 상에 코팅, 소프트-베이크(soft-bake), 노광, 현상 및 하드-베이크(hard-bake)하여 감광성 수지막을 형성하고, 이러한 일련의 과정을 착색제의 색상별로 반복하여 컬러 필터를 완성할 수 있다. 감광성 수지막의 형성 순서는 녹색(green) → 청색(blue) → 적색(red)의 순서; 또는 녹색(green) → 적색(red) → 청색(blue)의 순서가 일반적이다.A photosensitive resin composition containing a colorant of a specific color is coated, soft-baked, exposed, developed, and hard-baked on a substrate or a patterned photosensitive resin film thereon. A color filter can be completed by forming a film and repeating this series of processes for each color of the colorant. The order of formation of the photosensitive resin film is green → blue → red; Or the general order is green → red → blue.
상기 코팅은 스핀 코팅 방식을 이용하여 진행되는 것이 일반적이나, 해당 방식은 여러 문제를 야기한다. 구체적으로, 코팅 방식 상의 한계로 두께 균일도가 낮거나, 하부 감광성 수지막의 패턴에 의한 영향으로 광 산란, 색 불균일, 사선 불량 등이 나타나기도 한다. 특히, CIS용 컬러 필터는 박막으로 구현되므로, 코팅 과정에서 이물이 혼입될 경우 결함이 유발되어, 제품의 수율이 저하되기도 한다.The coating is generally performed using a spin coating method, but this method causes several problems. Specifically, thickness uniformity may be low due to limitations in the coating method, or light scattering, color unevenness, and diagonal defects may appear due to the influence of the pattern of the lower photosensitive resin film. In particular, since the color filter for CIS is implemented as a thin film, if foreign substances are mixed during the coating process, defects may occur and the yield of the product may decrease.
한편, 감광성 수지 조성물 내 용매의 휘발성이 높을수록, 상기 코팅 과정에서 건조 속도가 빨라지는 이점이 있다. 다만, 용매의 휘발성이 지나치게 높아 코팅 표면뿐만 아니라 하부에서도 휘발이 진행된다면, 이에 따라 형성되는 감광성 수지막에서 색 불균일, 두께 불균일 등이 나타날 수 있다.Meanwhile, the higher the volatility of the solvent in the photosensitive resin composition, the faster the drying speed during the coating process. However, if the volatility of the solvent is too high and volatilization occurs not only on the coating surface but also on the lower part, color unevenness, thickness unevenness, etc. may appear in the resulting photosensitive resin film.
이와 달리, 감광성 수지 조성물 내 용매의 휘발성이 낮을수록, 상기 코팅 과정에서 건조 속도가 느려질 수 있고, 장시간의 건조 과정에서 착색제 입자가 불균일해지거나 이물질이 혼입되면, 이에 따라 형성되는 감광성 수지막에서 사선 불량, 이물 등이 나타날 수 있다.On the other hand, the lower the volatility of the solvent in the photosensitive resin composition, the slower the drying speed may be during the coating process, and if the colorant particles become uneven or foreign substances are incorporated during the long-term drying process, the diagonal lines in the resulting photosensitive resin film may appear. Defects, foreign substances, etc. may appear.
상기 일 구현예는, 감광성 수지막의 색 및 두께를 균일하게 형성하면서도 사선 불량 및 이물을 억제할 수 있는 감광성 수지 조성물을 제공하기 위한 것이다.The above embodiment is intended to provide a photosensitive resin composition that can suppress diagonal defects and foreign substances while uniformly forming the color and thickness of the photosensitive resin film.
일반적으로 물질의 인화점이 높을수록 비점은 높아지고 휘발성은 낮아지는 경향이 있다. 상기 일 구현예의 감광성 수지 조성물은 인화점이 서로 다른 3종의 용매를 포함에 따라, 용매의 휘발 속도 및 휘발 위치를 조화롭게 제어할 수 있다. In general, the higher the flash point of a substance, the higher its boiling point and the lower its volatility. Since the photosensitive resin composition of the above embodiment includes three types of solvents with different flash points, the volatilization rate and volatilization position of the solvents can be controlled harmoniously.
그 결과, 녹색(green) 단독 또는 녹색(green) 및 적색(red)의 순서로 패턴화된 상태에서 청색(blue)의 감광성 수지막을 형성할 때, 용매의 휘발이 코팅 하부보다는 표면에서 주로 이루어지도록 하여, 청색(blue)의 채움 특성, 표면 거칠기(roughness) 등을 개선하여, 색 균일도, 두께 균일도 등을 향상시킬 수 있다. 또한, 용매의 휘발이 적절한 속도로 진행되도록 함에 따라, 감광성 수지막의 사선 불량 및 이물을 억제할 수 있다.As a result, when forming a blue photosensitive resin film with green alone or patterned in the order of green and red, the volatilization of the solvent occurs mainly at the surface rather than at the bottom of the coating. Thus, blue filling characteristics, surface roughness, etc. can be improved, and color uniformity and thickness uniformity can be improved. Additionally, by allowing volatilization of the solvent to proceed at an appropriate rate, defective diagonal lines and foreign matter in the photosensitive resin film can be suppressed.
이하, 상기 일 구현예의 감광성 수지 조성물을 상세히 설명한다.Hereinafter, the photosensitive resin composition of one embodiment will be described in detail.
[(E) 용매][(E) Solvent]
제1 용매 내지 제3 용매의 관계Relationship between first solvent and third solvent
상기 일 구현예의 감광성 수지 조성물은, 상기 제1 용매, 상기 제2 용매 및 상기 제3 용매를 각각 적어도 1종씩 포함하는 용매를 사용함에 따라, 색 및 두께가 균일하면서 사선 불량 및 이물이 억제된 감광성 수지막을 형성할 수 있다.The photosensitive resin composition of one embodiment has uniform color and thickness while suppressing diagonal defects and foreign matter by using a solvent containing at least one each of the first solvent, the second solvent, and the third solvent. A resin film can be formed.
구체적으로, 상기 용매 중에서, 인화점이 가장 낮아 휘발성이 가장 높은 제1 용매가 주 용매(main solvent)로서 함량이 가장 높고, 상기 제2 용매 및 제3 용매는 보조 용매(auxiliary solvent)로서 상기 제1 용매에 대비하여 함량이 적을 수 있다.Specifically, among the solvents, the first solvent with the lowest flash point and highest volatility is the main solvent and has the highest content, and the second and third solvents are auxiliary solvents, which are the first solvent. The content may be less compared to the solvent.
특히, 상기 제1 용매, 상기 제2 용매 및 상기 제3 용매는 하기 수학식 1을 만족할 수 있다:In particular, the first solvent, the second solvent, and the third solvent may satisfy Equation 1 below:
[수학식 1][Equation 1]
M1 > (M2+M3)M1 > (M2+M3)
상기 수학식 1에서, M1은 상기 제1 용매의 중량이고, M2는 상기 제2 용매의 중량이고, M3는 상기 제3 용매의 중량이다.In Equation 1, M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.
한편, 인화점이 가장 높아 휘발성이 가장 낮은 제3 용매의 함량이 가장 적고, 인화점이 가장 낮아 휘발성이 가장 높은 제1 용매의 함량은 상기 제3 용매의 함량보다 높으며, 인화점과 휘발성이 중간 수준인 제2 용매의 함량은 상기 제1 용매의 함량과 비슷하거나 그보다 더 적을 수 있다.Meanwhile, the content of the third solvent with the highest flash point and lowest volatility is the lowest, the content of the first solvent with the lowest flash point and highest volatility is higher than the content of the third solvent, and the content of the third solvent with the lowest flash point and volatility is intermediate. 2 The content of the solvent may be similar to or less than the content of the first solvent.
보다 구체적으로, 상기 용매의 총 중량 100 중량부 중에서, 상기 제1 용매는 40 중량부 이상 내지 80 중량부 이하, 50 중량부 이상 내지 80 중량부 이하, 또는 55 중량부 이상 내지 80 중량부 이하로 포함되고; 상기 제2 용매는 1 중량부 이상 내지 50 중량부 이하, 5 중량부 이상 내지 40 중량부 이하, 또는 10 중량부 이상 내지 30 중량부 이하로 포함되고; 상기 제3 용매는 0.1 중량부 이상 내지 40 중량부 이하, 또는 1 중량부 이상 내지 30 중량부 이하로 포함될 수 있다.More specifically, of the total weight of 100 parts by weight of the solvent, the first solvent is 40 parts by weight or more and 80 parts by weight or less, 50 parts by weight or more and 80 parts by weight or less, or 55 parts by weight or more and 80 parts by weight or less. Included; The second solvent is included in an amount of 1 part by weight or more and 50 parts by weight or less, 5 parts by weight or more and 40 parts by weight or less, or 10 parts by weight or more and 30 parts by weight or less; The third solvent may be included in an amount of 0.1 part by weight or more and 40 parts by weight or less, or 1 part by weight or more and 30 parts by weight or less.
특히, 상기 제1 용매의 함량은 55 중량부 이상 내지 80 중량부 이하에 가까울수록; 상기 제2 용매의 함량은 10 중량부 이상 내지 30 중량부 이하에 가까울수록; 상기 제3 용매는 1 중량부 이상 내지 10 중량부 이하에 가까울수록, 상기 제1 내지 제3 용매에 의한 시너지 효과가 향상될 수 있다.In particular, the closer the content of the first solvent is to 55 parts by weight or more to 80 parts by weight or less; The closer the content of the second solvent is to 10 parts by weight or more to 30 parts by weight or less; The closer the third solvent is to 1 part by weight or more to 10 parts by weight or less, the better the synergy effect of the first to third solvents.
상기 제1 내지 제3 용매의 총량은, 상기 감광성 수지 조성물 중 5 중량% 내지 70 중량%, 예컨대 40 중량% 내지 50 중량%로 포함될 수 있다. 상기 용매가 상기 범위 내로 포함될 경우 감광성 수지 조성물의 도포성이 우수하고, 평탄성이 우수한 도막을 얻을 수 있다.The total amount of the first to third solvents may be 5% to 70% by weight, for example, 40% to 50% by weight of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has excellent applicability and a coating film with excellent flatness can be obtained.
제1 용매first solvent
상기 제1 용매는 인화점이 40 ℃ 미만, 20 ℃ 이상 내지 35 ℃ 이하, 또는 25 ℃ 이상 내지 35 ℃ 이하일 수 있다. 또한, 상기 제1 용매는 1 atm 하에서 비점이 114 ℃ 이상 내지 138 ℃ 미만, 118 ℃ 이상 내지 134 ℃ 이하, 또는 122 ℃ 이상 내지 130 ℃ 이하일 수 있다.The first solvent may have a flash point of less than 40°C, 20°C or higher to 35°C or lower, or 25°C or higher to 35°C or lower. Additionally, the first solvent may have a boiling point of 114°C or higher to 138°C, 118°C or higher to 134°C or lower, or 122°C or higher to 130°C or lower at 1 atm.
상기 인화점 및 비점을 가지는 제1 용매는 아세테이트계 제1 용매 또는 알코올계 제1 용매일수 있다. 예컨대, 상기 제1 용매는 아세테이트계 제1 용매로서, n-부틸 아세테이트(n-butyl acetate, n-BA)일 수 있다.The first solvent having the flash point and boiling point may be an acetate-based first solvent or an alcohol-based first solvent. For example, the first solvent is an acetate-based first solvent and may be n-butyl acetate (n-BA).
상기 제1 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하, 4 중량% 이상 내지 40 중량% 이하, 또는 25 중량% 이상 내지 40 중량% 이하로 포함될 수 있다.The first solvent may be included in 1% by weight to 50% by weight, 4% by weight to 40% by weight, or 25% by weight to 40% by weight based on 100% by weight of the photosensitive resin composition.
제2 용매secondary solvent
상기 제2 용매는 인화점이 40 ℃ 이상 내지 60 ℃ 미만, 40 ℃ 이상 내지 55 ℃ 이하, 또는 40 ℃ 이상 내지 50 ℃ 이하일 수 있다. 또한, 상기 제2 용매는 1 atm 하에서 비점이 125 ℃ 이상 내지 150 ℃ 미만, 130 ℃ 이상 내지 149 ℃ 이하, 또는 140 ℃ 이상 내지 148 ℃ 이하일 수 있다.The second solvent may have a flash point of 40°C or higher to less than 60°C, 40°C or higher to 55°C or lower, or 40°C or higher to 50°C or lower. Additionally, the second solvent may have a boiling point of 125°C to 150°C, 130°C to 149°C, or 140°C to 148°C at 1 atm.
상기 인화점 및 비점을 가지는 제2 용매는 아세테이트계 제2 용매일 수 있다. 예컨대, 상기 제2 용매는 아세테이트계 제2 용매로서, 프로필렌 글리콜 모노메틸 에테르 아세테이트(propylene glycol monomethyl ether acetate, PGMEA), 에틸렌글리콜 모노 메틸 에테르 아세테이트(Ethylene glycol monomethyl ether acetate, EGMEA), 또는 이들의 조합일 수 있다.The second solvent having the flash point and boiling point may be an acetate-based second solvent. For example, the second solvent is an acetate-based second solvent, such as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate (EGMEA), or a combination thereof. It can be.
상기 제2 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하, 4 중량% 이상 내지 40 중량% 이하, 또는 4 중량% 이상 내지 15 중량% 이하로 포함될 수 있다.The second solvent may be included in 1% by weight to 50% by weight, 4% by weight to 40% by weight, or 4% by weight to 15% by weight based on 100% by weight of the photosensitive resin composition.
제3 용매tertiary solvent
상기 제3 용매는 인화점이 65 ℃ 이상, 65 ℃ 이상 내지 89 ℃ 이하, 또는 65 ℃ 이상 내지 85 ℃ 이하일 수 있다. 또한, 상기 제3 용매는 1 atm 하에서 비점이 150 ℃ 이상, 160 ℃ 이상 내지 190 ℃ 이하, 또는 170 ℃ 이상 내지 180 ℃ 이하일 수 있다.The third solvent may have a flash point of 65°C or higher, 65°C or higher to 89°C or lower, or 65°C or higher to 85°C or lower. Additionally, the third solvent may have a boiling point of 150°C or higher, 160°C or higher to 190°C or lower, or 170°C or higher to 180°C or lower at 1 atm.
상기 인화점 및 비점을 가지는 제3 용매는 2개 이상의 에테르기를 포함하는 구조를 가질 수 있다. 예컨대, 상기 제3 용매는 디에틸렌 글리콜 메틸 에틸 에테르(Diethylene glycol methyl ethyl ether, MEDG)일 수 있다.The third solvent having the flash point and boiling point may have a structure containing two or more ether groups. For example, the third solvent may be diethylene glycol methyl ethyl ether (MEDG).
상기 제3 용매는 상기 감광성 수지 조성물 100 중량% 중 0.1 중량% 이상 내지 25 중량% 이하, 0.1 중량% 이상 내지 20 중량% 이하, 또는 0.4 중량% 이상 내지 15 중량% 이하로 포함될 수 있다.The third solvent may be included in 0.1% by weight to 25% by weight, 0.1% by weight to 20% by weight, or 0.4% by weight to 15% by weight based on 100% by weight of the photosensitive resin composition.
[(A) 광중합성 화합물][(A) Photopolymerizable compound]
상기 광중합성 화합물은 적어도 1개의 에틸렌성 불포화 이중결합을 가지는 (메타)아크릴산의 일관능 또는 다관능 에스테르가 사용될 수 있다.The photopolymerizable compound may be a mono- or multi-functional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.
광중합성 화합물은 상기 에틸렌성 불포화 이중결합을 가짐으로써,　패턴 형성 공정에서 노광 시 충분한 중합을 일으킴으로써 내열성, 내광성 및 내화학성이 우수한 패턴을 형성할 수 있다.By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern with excellent heat resistance, light resistance, and chemical resistance by sufficiently polymerizing the compound upon exposure to light in the pattern formation process.
광중합성 화합물의 구체적인 예로는, 에틸렌 글리콜 디(메타)아크릴레이트, 디에틸렌 글리콜 디(메타)아크릴레이트, 트리에틸렌 글리콜 디(메타)아크릴레이트, 프로필렌 글리콜 디(메타)아크릴레이트, 네오펜틸 글리콜 디(메타)아크릴레이트, 1,4-부탄디올 디(메타)아크릴레이트, 1,6-헥산디올 디(메타)아크릴레이트, 비스페놀A 디(메타)아크릴레이트, 펜타에리트리톨 디(메타)아크릴레이트, 펜타에리트리톨 트리(메타)아크릴레이트, 펜타에리트리톨 테트라(메타)아크릴레이트, 펜타에리트리톨 헥사(메타)아크릴레이트, 디펜타에리트리톨 디(메타)아크릴레이트, 디펜타에리트리톨 트리(메타)아크릴레이트, 디펜타에리트리톨 펜타(메타)아크릴레이트, 디펜타에리트리톨 헥사(메타)아크릴레이트,　비스페놀A 에폭시(메타)아크릴레이트, 에틸렌 글리콜 모노메틸에테르 (메타)아크릴레이트, 트리메틸올 프로판 트리(메타)아크릴레이트, 트리스(메타)아크릴로일옥시에틸 포스페이트, 노볼락에폭시 (메타)아크릴레이트 등을 들 수 있다. Specific examples of photopolymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 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, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Rate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate ) acrylate, tris (meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, etc.
광중합성 화합물의 시판되는 제품을 예로 들면 다음과 같다. 상기 (메타)아크릴산의 일관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-101®, 동 M-111®, 동 M-114® 등; 니혼 가야꾸(주)社의 KAYARAD TC-110S®, 동 TC-120S® 등; 오사카 유끼 가가꾸 고교(주)社의 V-158®, V-2311® 등을 들 수 있다. 상기 (메타)아크릴산의 이관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-210®, 동 M-240®, 동 M-6200® 등; 니혼 가야꾸(주)社의 KAYARAD HDDA®, 동 HX-220®, 동 R-604® 등; 오사카 유끼 가가꾸 고교(주)社의 V-260®, V-312®, V-335 HP® 등을 들 수 있다. 상기 (메타)아크릴산의 삼관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-309®, 동 M-400®, 동 M-405®, 동 M-450®, 동 M-710®, 동 M-8030®, 동 M-8060® 등; 니혼 가야꾸(주)社의 KAYARAD TMPTA®, 동 DPCA-20®, 동-30®, 동-60®, 동-120® 등; 오사카 유끼 가야꾸 고교(주)社의 V-295®, 동-300®, 동-360®, 동-GPT®, 동-3PA®, 동-400® 등을 들 수 있다. 상기 제품을 단독 사용 또는 2종 이상 함께 사용할 수 있다.Examples of commercially available photopolymerizable compounds are as follows. Examples of the monofunctional ester of (meth)acrylic acid include Aronix M- 101® , M- 111® , and M- 114® manufactured by Toagosei Chemical Co., Ltd.; Nippon Kayaku Co., Ltd.'s KAYARAD TC-110S ® , KAYARAD TC-120S ® , etc.; Examples include V-158 ® and V-2311 ® manufactured by Osaka Yuki Chemical Co., Ltd. Examples of the above-mentioned difunctional ester of (meth)acrylic acid include Aronics M-210 ® , M-240 ® , and M-6200 ® manufactured by Toagosei Chemical Co., Ltd.; Nihon Kayaku Co., Ltd.'s KAYARAD HDDA ® , HX-220 ® , R-604 ® , etc.; Examples include V-260 ® , V-312 ® , and V-335 HP ® manufactured by Osaka Yuki Chemical Engineering Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronics M-309 ® , M-400 ® , M-405 ® , M-450 ® , and M manufactured by Toagosei Chemical Co., Ltd. -710 ® , M-8030 ® , M-8060 ® , etc.; Nippon Kayaku Co., Ltd.'s KAYARAD TMPTA ® , DPCA-20 ® , Dong-30 ® , Dong-60 ® , Dong-120 ® , etc.; Examples include V-295 ® , Dong-300 ® , Dong-360 ® , Dong-GPT ® , Dong-3PA ® , and Dong-400 ® manufactured by Osaka Yuki Kayaku Kogyo Co., Ltd. The above products can be used alone or in combination of two or more types.
상기 광중합성 화합물은 보다 우수한 현상성을 부여하기 위하여 산무수물로 처리하여 사용할 수도 있다.The photopolymerizable compound may be used by treating it with an acid anhydride to provide better developability.
상기 광중합성 화합물은 상기 감광성 수지 조성물 총량에 대하여 0.1 중량% 내지 20 중량%, 구체적으로 1 중량% 내지 15 중량%, 예컨대 2 중량% 내지 13 중량%로 포함될 수 있다. 광중합성 화합물이 상기 범위 내로 포함될 경우,　패턴 형성 공정에서 노광 시 경화가 충분히 일어나 신뢰성이 우수하며, 알칼리 현상액에의 현상성이 우수하다.The photopolymerizable compound may be included in an amount of 0.1% to 20% by weight, specifically 1% to 15% by weight, for example, 2% to 13% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure to light in the pattern formation process, resulting in excellent reliability and excellent developability in an alkaline developer.
[(B) 광중합 개시제][(B) Photopolymerization initiator]
상기 광중합 개시제는 감광성 수지 조성물에 일반적으로 사용되는 개시제로서, 예를 들어 아세토페논계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 벤조인계 화합물, 트리아진계 화합물, 옥심계 화합물 또는 이들의 조합을 사용할 수 있다. The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, 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. You can use it.
상기 아세토페논계 화합물의 예로는, 2,2'-디에톡시 아세토페논, 2,2'-디부톡시 아세토페논, 2-히드록시-2-메틸프로피오페논, p-t-부틸트리클로로 아세토페논, p-t-부틸디클로로 아세토페논, 4-클로로 아세토페논, 2,2'-디클로로-4-페녹시 아세토페논, 2-메틸-1-(4-(메틸티오)페닐)-2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온 등을 들 수 있다.Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.
상기 벤조페논계 화합물의 예로는, 벤조페논, 벤조일 안식향산, 벤조일 안식향산 메틸, 4-페닐 벤조페논, 히드록시 벤조페논, 아크릴화 벤조페논, 4,4'-비스(디메틸 아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 4,4'-디메틸아미노벤조페논, 4,4'-디클로로벤조페논, 3,3'-디메틸-2-메톡시벤조페논 등을 들 수 있다.Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.
상기 티오크산톤계 화합물의 예로는, 티오크산톤, 2-메틸티오크산톤, 이소프로필 티오크산톤, 2,4-디에틸 티오크산톤, 2,4-디이소프로필 티오크산톤, 2-클로로티오크산톤 등을 들 수 있다.Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.
상기 벤조인계 화합물의 예로는, 벤조인, 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 이소프로필 에테르, 벤조인 이소부틸 에테르, 벤질디메틸케탈 등을 들 수 있다.Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.
상기 트리아진계 화합물의 예로는, 2,4,6-트리클로로-s-트리아진, 2-페닐 4,6-비스(트리클로로메틸)-s-트리아진, 2-(3', 4'-디메톡시스티릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4'-메톡시나프틸)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-비페닐 4,6-비스(트리클로로 메틸)-s-트리아진, 비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-4-비스(트리클로로메틸)-6-피페로닐-s-트리아진, 2-4-비스(트리클로로메틸)-6-(4-메톡시스티릴)-s-트리아진 등을 들 수 있다.Examples of the triazine-based 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, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-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, etc.
상기 옥심계 화합물의 예로는, O-아실옥심계 화합물, 2-(o-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온, 1-(o-아세틸옥심)-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄온, O-에톡시카르보닐-α-옥시아미노-1-페닐프로판-1-온 등을 사용할 수 있다. 상기 O-아실옥심계 화합물의 구체적인 예로는, 1,2-옥탄디온, 2-디메틸아미노-2-(4-메틸벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온, 1-(4-페닐술파닐페닐)-부탄-1,2-디온2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1,2-디온2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1-온옥심-O-아세테이트 및 1-(4-페닐술파닐페닐)-부탄-1-온옥심-O-아세테이트 등을 들 수 있다. Examples of the oxime-based compounds include O-acyloxime-based 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, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2 -oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime-O- Acetate, etc. can be mentioned.
상기 광중합 개시제는 상기 화합물 이외에도 카바졸계 화합물, 디케톤류 화합물, 술포늄 보레이트계 화합물, 디아조계 화합물, 이미다졸계 화합물, 비이미다졸계 화합물, 플루오렌계 화합물 등을 사용할 수 있다.In addition to the above compounds, the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and fluorene-based compounds.
상기 광중합 개시제는 빛을 흡수하여 들뜬 상태가 된 후 그 에너지를 전달함으로써 화학반응을 일으키는 광 증감제와 함께 사용될 수도 있다.The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.
상기 광 증감제의 예로는, 테트라에틸렌글리콜 비스-3-머캡토 프로피오네이트, 펜타에리트리톨 테트라키스-3-머캡토 프로피오네이트, 디펜타에리트리톨 테트라키스-3-머캡토 프로피오네이트 등을 들 수 있다. Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.
상기 광중합 개시제는 상기 감광성 수지 조성물 총량에 대하여 0.1 중량% 내지 5 중량%, 구체적으로 0.3 중량% 내지 4.5 중량%, 예컨대 0.5 중량% 내지 4 중량%로 포함될 수 있다. 광중합 개시제가 상기 범위 내로 포함될 경우, 패턴 형성 공정에서 노광시 경화가 충분히 일어나 우수한 신뢰성을 얻을 수 있으며, 패턴의 내열성, 내광성 및 내화학성이 우수하고, 해상도 및 밀착성 또한 우수하며, 미반응 개시제로 인한 투과율의 저하를 막을 수 있다.The photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, specifically 0.3% by weight to 4.5% by weight, for example, 0.5% by weight to 4% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure during the pattern formation process to obtain excellent reliability, the heat resistance, light resistance, and chemical resistance of the pattern are excellent, resolution and adhesion are also excellent, and there is no damage from unreacted initiators. Deterioration of transmittance can be prevented.
[(C) 착색제][(C) Colorant]
상기 착색제는 안료를 포함할 수 있고, 이때 상기 일 구현예의 수지 조성물은 안료형 조성물이 될 수 있다. 상기 안료로는 녹색 안료, 청색 안료, 적색 안료, 자색 안료, 황색 안료, 흑색 안료 등을 사용할 수 있다.The colorant may include a pigment, and in this case, the resin composition of one embodiment may be a pigment-type composition. As the pigment, green pigment, blue pigment, red pigment, purple pigment, yellow pigment, black pigment, etc. can be used.
상기 적색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 적색 안료 254, C.I. 적색 안료 255, C.I. 적색 안료 264, C.I. 적색 안료 270, C.I. 적색 안료 272, C.I. 적색 안료 177, C.I. 적색 안료 89 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The red pigment is classified as C.I. in the color index. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89, etc. can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
　상기　자색　안료는 컬러 인덱스(Color Index) 내에서 C.I.　 바이올렛 안료 23(V.23), C.I.　바이올렛　안료　29, 디옥사진　바이올렛, 퍼스트　바이올렛　B, 메틸　바이올렛　레이크, 인단트렌 브릴리언트　바이올렛　등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The purple pigment is C.I. within the Color Index. Violet Pigment 23 (V.23), C.I. Violet Pigment 29, Dioxazine Violet, First Violet B, Methyl Violet Lake, Indanthrene Brilliant Violet, etc. can be used, and these can be used alone or in a mixture of two or more, but are not necessarily limited thereto.
상기 녹색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 녹색 안료 7, C.I. 녹색 안료 36, C.I. 녹색 안료 58, C.I. 녹색 안료 59 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The green pigment is classified as C.I. in the color index. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green pigment 59, etc. can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
상기 청색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 청색 안료 15:6, C.I. 청색 안료 15, C.I. 청색 안료 15:1, C.I. 청색 안료 15:2, C.I. 청색 안료 15:3, C.I. 청색 안료 15:4, C.I. 청색 안료 15:5, C.I. 청색 안료 15:6, C.I. 청색 안료 16 등과 같은 구리 프탈로시아닌 안료를 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The blue pigment is C.I. in the color index. Blue pigment 15:6, C.I. Blue Pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. Blue pigment 15:6, C.I. Copper phthalocyanine pigments such as blue pigment 16 can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
상기 황색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 황색 안료 185, C.I. 황색 안료 139 등과 같은 이소인돌린계 안료, C.I. 황색 안료 138 등과 같은 퀴노프탈론계 안료, C.I. 황색 안료 150 등과 같은 니켈 컴플렉스 안료 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The yellow pigment is classified as C.I. in the color index. Yellow Pigment 185, C.I. Isoindoline pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. Nickel complex pigments such as yellow pigment 150 can be used, and these can be used alone or in a mixture of two or more types, but are not necessarily limited thereto.
상기 흑색 안료는 컬러 인덱스(Color Index) 내에서 아닐린 블랙, 퍼릴렌 블랙, 티타늄 블랙, 카본 블랙 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The black pigment may include aniline black, perylene black, titanium black, and carbon black within the color index, and may be used alone or in a mixture of two or more types, but is not necessarily limited thereto.
상기 안료는 이들을 단독으로 또는 둘 이상 혼합하여 사용할 수 있다. 예컨대, 상기 안료로는 청색 안료, 자색 안료 또는 이들의 혼합물을 사용할 수 있다.The above pigments can be used alone or in a mixture of two or more. For example, the pigment may be a blue pigment, a purple pigment, or a mixture thereof.
상기 안료는 분산액 형태로 컬러 필터용 감광성 수지 조성물에 포함될 수 있다. 　이러한 안료 분산액은 상기 안료와 용매, 분산제, 분산수지 등으로 이루어질 수 있다. 상기 고형분의 안료는 상기 안료분산액 총량에 대해 5 중량% 내지 20 중량%, 예컨대 8 중량% 내지 15 중량%로 포함될 수 있다.The pigment may be included in the photosensitive resin composition for a color filter in the form of a dispersion. This pigment dispersion may be composed of the pigment, solvent, dispersant, dispersion resin, etc. The solid pigment may be included in an amount of 5% to 20% by weight, for example, 8% to 15% by weight, based on the total amount of the pigment dispersion.
상기 용매로는 에틸렌 글리콜 아세테이트, 에틸 셀로솔브, 프로필렌 글리콜 메틸 에테르 아세테이트, 에틸 락테이트, 폴리에틸렌 글리콜, 사이클로헥사논, 프로필렌 글리콜 메틸 에테르 등을 사용할 수 있으며, 이들 중에서 좋게는 프로필렌 글리콜 메틸 에테르 아세테이트를 사용할 수 있다. The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. Among these, propylene glycol methyl ether acetate is preferred. You can.
상기 분산제는 상기 안료가 분산액 내에 균일하게 분산되도록 도와주며, 비이온성, 음이온성 또는 양이온성의 분산제 각각 사용할 수 있다. 구체적으로는 폴리알킬렌 글리콜 또는 이의 에스테르, 폴리옥시 알킬렌, 다가 알콜 에스테르 알킬렌 옥사이드 부가물, 알코올 알킬렌 옥사이드 부가물, 술폰산 에스테르, 술폰산 염, 카르복시산 에스테르, 카르복시산 염, 알킬 아미드 알킬렌 옥사이드 부가물, 알킬 아민 등을 사용할 수 있으며, 이들은 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The dispersant helps the pigment to be uniformly dispersed in the dispersion, and nonionic, anionic, or cationic dispersants can be used. Specifically, polyalkylene glycol or its ester, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide addition. Water, alkyl amine, etc. can be used, and these can be used alone or in a mixture of two or more types.
상기 분산수지는 카르복시기를 포함한 아크릴계 수지를 사용할 수 있으며, 이는 안료 분산액의 안정성을 향상시킬 수 있을 뿐만 아니라 픽셀의 패턴성도 개선시킬 수 있다.The dispersion resin may be an acrylic resin containing a carboxyl group, which can not only improve the stability of the pigment dispersion but also improve the patterning of the pixel.
상기 착색제는 상기 안료를 포함하면서, 염료를 더 포함할 수 있고, 이때 상기 일 구현예의 수지 조성물은 하이브리드형 조성물이 될 수 있다. 또한, 상기 염료는 특별히 한정하지 않지만, 금속 착체 염료를 포함할 수 있다.The colorant may include the pigment and may further include a dye, and in this case, the resin composition of the embodiment may be a hybrid composition. Additionally, the dye is not particularly limited, but may include a metal complex dye.
상기 금속 착체　염료는 200 nm 내지 650 nm 파장 영역에서 최대 흡광도를 갖는 화합물을 사용할 수 있고, 색소의 조합에 색좌표를 맞추기 위해 상기 범위의 흡광도를 가지는 화합물이라면 유기용매에 녹는 모든 컬러의 금속 착체　염료를 사용할 수 있다.The metal complex dye can be a compound having a maximum absorbance in the wavelength range of 200 nm to 650 nm. In order to match the color coordinates of the combination of pigments, a metal complex dye of any color soluble in an organic solvent can be used as long as it has an absorbance in the above range. You can use it.
구체적으로, 상기 금속 착체　염료는, 530 nm 내지 680 nm 파장 영역에서 최대 흡광도를 갖는 녹색 염료, 200 nm 내지 400 nm 파장 영역에서 최대 흡광도를 갖는 황색　염료, 300 nm 내지 500 nm 파장 영역에서 최대 흡광도를 갖는 오렌지　염료, 500 nm 내지 650 nm 파장 영역에서 최대 흡광도를 갖는 적색　염료　또는 이들의 조합을 사용할 수 있다.Specifically, the metal complex dye includes a green dye with maximum absorbance in the 530 nm to 680 nm wavelength range, a yellow dye with maximum absorbance in the 200 nm to 400 nm wavelength range, and a maximum absorbance in the 300 nm to 500 nm wavelength range. An orange dye with a maximum absorbance in the wavelength range of 500 nm to 650 nm, a red dye with a maximum absorbance, or a combination thereof can be used.
상기 금속 착체　염료는 직접　염료, 산성　염료, 염기성　염료, 산성 매염　염료, 황화　염료, 환원　염료, 아조익　염료, 분산　염료, 반응성　염료, 산화　염료, 유용　염료, 아조　염료, 안트라퀴논　염료, 인디고이드　염료, 카르보늄이온　염료,　프탈로시아닌　염료, 니트로　염료, 퀴놀린　염료, 시아닌　염료, 폴리메틴　염료　또는 이들의 조합을 사용할 수 있다.The above metal complex dyes include direct dyes, acidic dyes, basic dyes, acid mordant dyes, sulfuric dyes, reduced dyes, azoic dyes, disperse dyes, reactive dyes, oxidizing dyes, oil-soluble dyes, azo dyes, anthraquinone dyes, and indigoid dyes. , carbonium ion dye, phthalocyanine dye, nitro dye, quinoline dye, cyanine dye, polymethine dye, or a combination thereof can be used.
상기 금속 착체　염료는 Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd 및 Fe로 이루어진 군에서 선택된 적어도 하나의 금속 이온을 포함할 수 있다.The metal complex dye may include at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.
상기 금속 착체　염료는 C.I.　솔벤트　그린　1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 등의 C.I.　솔벤트　염료; C.I. 애시드　그린　1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 등의 C.I. 애시드 염료;　C.I. 다이렉트　그린　25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 등의 C.I. 다이렉트 염료, C.I. 베이직　그린　1 등의 C.I. 베이직 염료;C.I. 모던트　그린　1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 등의 C.I. 모던트 염료, C.I. 피그먼트　그린　7, 36, 58 등의 녹색 안료; 솔벤트 옐로우 19, 솔벤트 옐로우 21, 솔벤트 옐로우 25, 솔벤트 옐로우 79, 솔벤트 옐로우 82, 솔벤트 옐로우 88, 솔벤트 오렌지 45, 솔벤트 오렌지 54, 솔벤트 오렌지 62, 솔벤트 오렌지 99, 솔벤트 레드 8, 솔벤트 레드 32, 솔벤트 레드 109, 솔벤트 레드 112, 솔벤트 레드 119, 솔벤트 레드 124, 솔벤트 레드 160, 솔벤트 레드 132 및 솔벤트 레드 218로 이루어진 군에서 선택된 적어도 하나와 상기 금속 이온의 복합체를 사용할 수 있다.The metal complex dye is C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent, dye; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C.I.s such as 104, 105, 106, 109, etc. acid dye; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct dye, C.I. C.I. such as Basic, Green 1, etc. Basic dye;C.I. C.I. of Modernant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. Mordant Dye, C.I. Green pigments such as Pigment Green 7, 36, and 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 A complex of the metal ion and at least one selected from the group consisting of Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132, and Solvent Red 218 may be used.
상기 금속 착체을 포함하는　염료는 일 구현예에 따른 감광성 수지 조성물에 사용되는 용매, 즉, 후술하는 용매에 대한 용해도가 5 이상일 수 있고, 구체적으로는 5 내지 10 일 수 있다. 상기 용해도는 상기 용매 100g에 녹는 상기　염료의 양(g)으로 얻을 수 있다. 상기 금속 착체를 포함하는　염료의 용해도가 상기 범위 내일 경우, 일 구현예에 따른 감광성 수지 조성물을 이루는 다른 성분과의 상용성 및 착색력을 확보할 수 있고,　염료의 석출이 방지될 수 있다.The dye containing the metal complex may have a solubility in a solvent used in the photosensitive resin composition according to one embodiment, that is, a solvent described later, of 5 or more, specifically 5 to 10. The solubility can be obtained by the amount (g) of the dye dissolved in 100 g of the solvent. When the solubility of the dye containing the metal complex is within the above range, compatibility and coloring power with other components constituting the photosensitive resin composition according to one embodiment can be secured, and precipitation of the dye can be prevented.
상기 용매는, 예를 들어, 프로필렌 글리콜 모노메틸에테르 아세테이트(propylene glycol monomethyl ether acetate, PGMEA), 에틸 락테이트(ethyl lactate, EL), 에틸렌 글리콜 에틸 아세테이트(ethylene glycol ethyl acetate, EGA), 시클로헥사논(cyclohexanone), 3-메톡시-1-부탄올(3-methoxy-1-butanol) 또는 이들의 조합을 사용할 수 있다.The solvent is, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone. (cyclohexanone), 3-methoxy-1-butanol (3-methoxy-1-butanol), or a combination thereof can be used.
상기 특정 범위를 가짐에 따라, 원하는 색좌표에서 고휘도 및 고명암비를 발현하는 LCD, LED 등의 컬러 필터에 유용하게 사용될 수 있다.By having the above specific range, it can be usefully used in color filters such as LCDs and LEDs that produce high brightness and high contrast ratio at desired color coordinates.
상기 금속 착체를 포함하는　염료는 상기 감광성 수지 조성물 총량에 대하여 0.01 중량% 내지 1 중량%, 예컨대 0.01 중량% 내지 0.5 중량%로 포함될 수 있다. 상기 금속 착체를 포함하는　염료를 상기 범위로 사용할 경우, 원하는 색좌표에서 높은 휘도 및 명암비를 발현할 수 있다.The dye containing the metal complex may be included in an amount of 0.01% by weight to 1% by weight, for example, 0.01% by weight to 0.5% by weight, based on the total amount of the photosensitive resin composition. When the dye containing the metal complex is used in the above range, high luminance and contrast ratio can be achieved at the desired color coordinate.
상기 염료 및 상기 안료를 혼합하여 사용할 경우 0.1:99.9 내지 99.9:0.1의 중량비, 구체적으로는 1:9 내지 9:1의 중량비로 혼합하여 사용할 수 있다. 상기 중량비 범위로 혼합할 경우 내화학성, 최대 흡수 파장을 적절한 범위로 제어하고, 원하는 색좌표에서 높은 휘도 및 명암비를 발현할 수 있다. When the dye and the pigment are mixed and used, they can be mixed at a weight ratio of 0.1:99.9 to 99.9:0.1, specifically 1:9 to 9:1. When mixed in the above weight ratio range, chemical resistance and maximum absorption wavelength can be controlled to an appropriate range, and high luminance and contrast ratio can be expressed at the desired color coordinate.
상기 착색제는 고형분 기준으로, 상기 감광성 수지 조성물 총량에 대하여 5 중량% 내지 50 중량%, 구체적으로 6 중량% 내지 40 중량%, 예컨대 7 중량% 내지 30 중량%로 포함될 수 있다. 상기 착색제가 상기 범위 내로 포함될 경우, 착색 효과 및 현상성이 우수하다.Based on solid content, the colorant may be included in an amount of 5% to 50% by weight, specifically 6% to 40% by weight, for example, 7% to 30% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the coloring effect and developability are excellent.
[(D) 바인더 수지][(D) Binder Resin]
상기 바인더 수지는 아크릴계 수지를 포함할 수 있다.The binder resin may include an acrylic resin.
상기 아크릴계 수지는 제1 에틸렌성 불포화 단량체　및 이와 공중합 가능한 제2 에틸렌성 불포화 단량체의 공중합체로, 하나 이상의 아크릴계 반복단위를 포함하는 수지이다.The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.
상기 제1 에틸렌성 불포화 단량체는 하나 이상의 카르복시기를 함유하는 에틸렌성 불포화 단량체이며, 이의 구체적인 예로는　아크릴산, 메타크릴산, 말레산, 이타콘산, 푸마르산 또는 이들의 조합을 들 수 있다.The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
상기 제1 에틸렌성 불포화 단량체는 상기 아크릴계 바인더 수지 총량에 대하여 5 중량% 내지 50 중량%, 예컨대 10 중량% 내지 40 중량%로 포함될 수 있다.The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, based on the total amount of the acrylic binder resin.
상기 제2 에틸렌성 불포화 단량체는 스티렌, α-메틸스티렌, 비닐톨루엔, 비닐벤질메틸에테르 등의 방향족 비닐 화합물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시 부틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 페닐(메타)아크릴레이트 등의 불포화 카르복시산 에스테르 화합물; 2-아미노에틸(메타)아크릴레이트, 2-디메틸아미노에틸(메타)아크릴레이트 등의 불포화 카르복시산 아미노 알킬 에스테르 화합물; 초산비닐, 안식향산 비닐 등의 카르복시산 비닐 에스테르 화합물; 글리시딜(메타)아크릴레이트 등의 불포화 카르복시산 글리시딜 에스테르 화합물; (메타)아크릴로니트릴 등의 시안화 비닐 화합물; (메타)아크릴아미드 등의 불포화 아미드 화합물; 등을 들 수 있으며, 이들을 단독으로 또는 둘 이상 혼합하여 사용할 수 있다.The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, Unsaturated carboxylic acid ester compounds such as 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; Carboxylic acid vinyl 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; Unsaturated amide compounds such as (meth)acrylamide; These can be mentioned, and these can be used alone or in a mixture of two or more.
상기 아크릴계 수지의 구체적인 예로는 (메타)아크릴산/벤질메타크릴레이트 공중합체, (메타)아크릴산/벤질메타크릴레이트/스티렌 공중합체, (메타)아크릴산/벤질메타크릴레이트/2-히드록시에틸메타크릴레이트 공중합체, (메타)아크릴산/벤질메타크릴레이트/스티렌/2-히드록시에틸메타크릴레이트 공중합체 등을 들 수 있으나, 이에 한정되는 것은 아니며, 이들을 단독 또는 2종 이상을 배합하여 사용할 수도 있다.Specific examples of the acrylic resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate Examples include, but are not limited to, late copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and these may be used alone or in combination of two or more types. .
상기 바인더 수지는 에폭시계 바인더 수지를 포함할 수 있다.The binder resin may include an epoxy-based binder resin.
상기 바인더 수지는 에폭시계 바인더 수지를 더 포함함으로써, 내열성을 향상시킬 수 있다. 상기 에폭시계 바인더 수지는 예컨대, 페놀 노볼락 에폭시 수지, 테트라메틸 비페닐 에폭시 수지, 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 지환족 에폭시 수지 또는 이들의 조합 등을 들 수 있으나, 이에 한정되는 것은 아니다.The binder resin can improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may include, for example, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, cycloaliphatic epoxy resin, or a combination thereof, but is limited thereto. That is not the case.
나아가, 상기 에폭시계 바인더 수지를 포함하는 바인더 수지는 후술할 안료 등의 착색제의 분산 안정성을 확보함과 동시에, 현상 과정에서 원하는 해상도의 픽셀이 형성되도록 돕는다. Furthermore, the binder resin containing the epoxy-based binder resin ensures the dispersion stability of colorants such as pigments, which will be described later, and helps form pixels with a desired resolution during the development process.
상기 에폭시계 바인더 수지는 상기 바인더 수지 총량에 대해 1 중량% 내지 10 중량%, 예컨대 5 중량% 내지 10 중량%로 포함될 수 있다. 상기 에폭시계 바인더 수지가 상기 범위로 포함될 경우, 잔막률 및 내화학성이 크게 개선될 수 있다.The epoxy-based binder resin may be included in an amount of 1% to 10% by weight, for example, 5% to 10% by weight, based on the total amount of the binder resin. When the epoxy-based binder resin is included in the above range, the remaining film rate and chemical resistance can be greatly improved.
상기 에폭시계 바인더 수지의 에폭시당량(epoxy equivalent weight)은 150 g/eq 내지 200 g/eq 일 수 있다. 상기 범위 내의 에폭시당량을 가지는 에폭시계 바인더 수지가 바인더 수지 내에 포함될 경우, 형성된 패턴의 경화도 향상 및 패턴이 형성된 구조 내에서의 착색제 고착에 유리한 효과가 있다.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 an advantageous effect in improving the curability of the formed pattern and fixing the colorant in the structure in which the pattern is formed.
상기 바인더 수지는 고형분 형태로 후술하는 용매에 용해되어, 감광성 수지 조성물을 구성할 수 있다. 이 경우, 상기 고형분 형태의 바인더 수지는 용매에 용해된 바인더 수지 용액 총량에 대해 약 0.1 중량% 내지 30 중량%, 예컨대 20 중량% 내지 30 중량% 일 수 있다.The binder resin may be dissolved in a solvent described later in solid form to form a photosensitive resin composition. In this case, the binder resin in the solid form may be about 0.1% by weight to 30% by weight, for example, 20% by weight to 30% by weight, based on the total amount of the binder resin solution dissolved in the solvent.
상기 바인더 수지는 고형분 기준으로, 상기 감광성 수지 조성물 총량에 대하여 0.1 중량% 내지 20 중량%, 구체적으로 0.5 중량% 내지 15 중량%, 예컨대 1 중량% 내지 10 중량%로 포함될 수 있다. 바인더 수지가 상기 범위 내로 포함될 경우, 컬러 필터 제조 시 현상성이 우수하며 가교성이 개선되어 우수한 표면 평활도를 얻을 수 있다.Based on solid content, the binder resin may be included in an amount of 0.1% to 20% by weight, specifically 0.5% to 15% by weight, for example, 1% to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability is excellent when manufacturing a color filter, crosslinking is improved, and excellent surface smoothness can be obtained.
[(F) 기타 첨가제][(F) Other additives]
상기 감광성 수지 조성물은 도포 시 얼룩이나 반점을 방지하고, 레벨링 성능을 개선하기 위해, 또한 미현상에 의한 잔사의 생성을 방지하기 위하여, 말론산; 3-아미노-1,2-프로판디올; 비닐기 또는 (메타)아크릴옥시기를 포함하는 커플링제; 레벨링제; 계면활성제; 및 라디칼 중합 개시제로부터 선택되는 적어도 하나의 첨가제를 더 포함할 수 있다.The photosensitive resin composition contains malonic acid to prevent stains or spots upon application, to improve leveling performance, and to prevent the creation of residues due to non-development; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or (meth)acryloxy group; leveling agent; Surfactants; and at least one additive selected from radical polymerization initiators.
상기 첨가제는 원하는 물성에 따라 용이하게 조절될 수 있다.The additives can be easily adjusted according to desired physical properties.
상기 커플링제는 실란계 커플링제일 수 있고, 상기 실란계 커플링제의 예로는, 트리메톡시실릴 벤조산, γ메타크릴 옥시프로필 트리메톡시실란, 비닐 트리아세톡시실란, 비닐 트리메톡시실란, γ이소 시아네이트 프로필 트리에톡시실란, γ글리시독시 프로필 트리메톡시실란, β에폭시사이클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 이들을 단독 또는 2종 이상 혼합하여 사용할 수 있다. The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Examples include isocyanate propyl triethoxysilane, γ glycidoxy propyl trimethoxysilane, and β epoxycyclohexyl)ethyltrimethoxysilane, and these can be used alone or in a mixture of two or more types.
상기 실란계 커플링제는 구체적으로 상기 감광성 수지 조성물 100 중량부에 대하여 0.01 중량부 내지 1 중량부로 사용될 수 있다.The silane-based coupling agent may be specifically used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.
또한 상기 컬러 필터용 감광성 수지 조성물은 필요에 따라 계면활성제, 예컨대 불소계 계면활성제를 더 포함할 수 있다. 　Additionally, the photosensitive resin composition for a color filter may further include a surfactant, such as a fluorine-based surfactant, if necessary.
상기 불소계 계면활성제의 예로는 DIC社의 F-482, F-484, F-478 등이 있으며, 이에 한정되는 것은 아니다.Examples of the fluorine-based surfactant include DIC's F-482, F-484, and F-478, but are not limited thereto.
상기 계면활성제는 감광성 수지 조성물 총량에 대하여 0.01 중량% 내지 5 중량%로 포함되는 것이 바람직하고 0.01 중량% 내지 2 중량%로 포함되는 것이 보다 바람직하다. 상기 범위를 벗어나는 경우 현상 후 이물질이 발생하는 문제점이 생길 수 있어 바람직하지 못하다.The surfactant is preferably contained in an amount of 0.01 wt% to 5 wt%, and more preferably in an amount of 0.01 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If it is outside the above range, it is undesirable because it may cause problems with foreign substances occurring after development.
또한 상기 감광성 수지 조성물은 물성을 저해하지 않는 범위 내에서 산화방지제, 안정제 등의 기타 첨가제가 일정량 첨가될 수도 있다.Additionally, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within the range that does not impair the physical properties.
(감광성 수지막, 컬러 필터 및 CMOS 이미지 센서)(Photosensitive resin film, color filter, and CMOS image sensor)
다른 일 구현예에 따르면, 일 구현예에 따른 감광성 수지 조성물을 이용하여 제조된 감광성 수지막을 제공한다.According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.
또 다른 일 구현예에 따르면 전술한 감광성 수지 조성물을 이용하여 제조된 컬러 필터를 제공한다. According to another embodiment, a color filter manufactured using the above-described photosensitive resin composition is provided.
상기 컬러 필터의 제조 방법은 다음과 같다. The manufacturing method of the color filter is as follows.
유리 기판 위에 스핀 도포, 롤러 도포, 스프레이 도포 등의 적당한 방법을 사용하여, 예를 들면, 0.1 ㎛ 내지 10 ㎛의 두께로 전술한 감광성 수지 조성물을 도포하여 감광성 수지 조성물 층을 형성한다.The photosensitive resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.1 μm to 10 μm, using an appropriate method such as spin coating, roller coating, or spray coating, on a glass substrate.
이어서, 상기 감광성 수지 조성물 층이 형성된 기판에 컬러 필터에 필요한 패턴을 형성하도록 광을 조사한다. 조사에 사용되는 광원으로는 UV, 전자선 또는 X선을 사용할 수 있고, 예를 들면, 190nm 내지 450nm, 구체적으로는 200nm 내지 400nm 영역의 UV를 조사할 수 있다. 상기 조사하는 공정에서 포토레지스트 마스크를 더욱 사용하여 실시할 수도 있다.　이와 같이 조사하는 공정을 실시한 후, 상기 광원이 조사된 감광성 수지 조성물 층을 현상액으로 처리한다. 이때 감광성 수지 조성물 층에서 비노광 부분은 용해됨으로써 컬러 필터에 필요한 패턴이 형성된다. 이러한 공정을 필요한 색의 수에 따라 반복함으로써 원하는 패턴을 갖는 컬러 필터를 수득할 수 있다. 또한 상기 공정에서 현상에 의해 수득된 화상 패턴을 다시 가열하거나 활성선 조사 등에 의해 경화시키면 내크랙성, 내용제성 등을 향상시킬 수 있다.Next, light is irradiated to the substrate on which the photosensitive resin composition layer is formed to form a pattern necessary for a color filter. As a light source used for irradiation, UV, electron beams, or The above irradiation process can also be performed by further using a photoresist mask. After performing this irradiation process, the photosensitive resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed portion of the photosensitive resin composition layer is dissolved, thereby forming a pattern required for the color filter. By repeating this process according to the number of colors required, a color filter with a desired pattern can be obtained. In addition, crack resistance, solvent resistance, etc. can be improved by heating the image pattern obtained through development in the above process again or curing it by irradiation with actinic rays.
또 다른 일 구현예에 따르면 상기 컬러 필터를 포함하는 CMOS　이미지　센서를 제공한다.According to another implementation, a CMOS image sensor including the color filter is provided.
이하, 실시예를 들어 본 발명에 대해서 더욱 상세하게 설명할 것이나, 하기의 실시예는 본 발명의 바람직한 실시예일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.
(감광성 수지 조성물의 제조)(Preparation of photosensitive resin composition)
실시예 1 내지 실시예 14 및 비교예 1 내지 비교예 6Examples 1 to 14 and Comparative Examples 1 to 6
표 1 내지 6에 나타낸 조성으로, 실시예 1 내지 실시예 14 및 비교예 1 내지 비교예 6의 각 감광성 수지 조성물을 제조하였다.With the compositions shown in Tables 1 to 6, the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6 were prepared.
구체적으로, 용매에 광중합 개시제를 녹인 후 상온에서 30분 동안 교반한 다음, 여기에 바인더 수지 및 광중합성 화합물을 첨가하여 상온에서 60분 동안 교반 하였다. 이어서, 착색제로서 염료 및 안료 분산액을 넣고 상온에서 30분 동안 교반하였다. 여기에 첨가제를 투입한 후, 1시간 동안 상온에서 교반하고, 3회 여과하여 불순물을 제거함으로써, 감광성　수지　조성물을 제조하였다. Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 30 minutes, then a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 60 minutes. Next, dye and pigment dispersion as a colorant were added and stirred at room temperature for 30 minutes. Additives were added here, stirred at room temperature for 1 hour, and filtered three times to remove impurities, thereby preparing a photosensitive resin composition.
(단위: 중량%)(Unit: weight%)
성분ingredient 재료명Material name 고형분
(%)solid content
(%) 		실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예
6Example
6 		실시예
7Example
7 		실시예
8Example
8
(A) 광중합성
화합물(A) Photopolymerization
compound 		A-1A-1 100100 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1
(B) 광중합
개시제(B) Light curing
initiator 		B-1B-1 100100 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
(C)
착색제(C)
coloring agent 		C-1C-1 1818 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5
C-2C-2 1818 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3
(D)
바인더
수지(D)
bookbinder
profit 		D-1D-1 3030 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4
(E)
용매(E)
menstruum 		E-1E-1 -- 4.84.8 9.69.6 14.414.4 19.219.2 2424 28.828.8 33.633.6 38.438.4
E-2E-2 -- 38.438.4 33.633.6 28.828.8 2424 19.219.2 14.414.4 9.69.6 4.84.8
E-3E-3 -- 4.84.8 4.84.8 4.84.8 4.84.8 4.84.8 4.84.8 4.84.8 4.84.8
E-4E-4 -- -- -- -- -- -- -- -- --
E-5E-5 -- -- -- -- -- -- -- -- --
E-6E-6 -- -- -- -- -- -- -- -- --
(F)
첨가제(F)
additive 		F-1F-1 1010 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
(단위: 중량%)(Unit: weight%)
성분ingredient 재료명Material name 고형분
(%)solid content
(%) 		실시예
9Example
9 		실시예
10Example
10 		실시예
6Example
6 		실시예
11Example
11 		실시예
12Example
12 		실시예
13Example
13 		실시예
14Example
14
(A) 광중합성
화합물(A) Photopolymerization
compound 		A-1A-1 100100 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1
(B) 광중합
개시제(B) Light curing
initiator 		B-1B-1 100100 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
(C)
착색제(C)
coloring agent 		C-1C-1 1818 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5
C-2C-2 1818 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3
(D)
바인더
수지(D)
bookbinder
profit 		D-1D-1 3030 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4
(E)
용매(E)
menstruum 		E-1E-1 -- 33.12
33.12
 		31.231.2 28.828.8 26.426.4 2424 21.621.6 19.219.2
E-2E-2 -- 14.414.4 14.414.4 14.414.4 14.414.4 14.414.4 14.414.4 14.414.4
E-3E-3 -- 0.480.48 2.42.4 4.84.8 7.27.2 9.69.6 1212 14.414.4
E-4E-4 -- -- -- -- -- -- -- --
E-5E-5 -- -- -- -- -- -- -- --
E-6E-6 -- -- -- -- -- -- -- --
(F)
첨가제(F)
additive 		F-1F-1 1010 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
(단위: 중량%)(Unit: weight%)
성분ingredient 재료명Material name 고형분
(%)solid content
(%) 		비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6
(A) 광중합성
화합물(A) Photopolymerization
compound 		A-1A-1 100100 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1 2.12.1
(B) 광중합
개시제(B) Light curing
initiator 		B-1B-1 100100 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
(C)
착색제(C)
coloring agent 		C-1C-1 1818 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5 31.531.5
C-2C-2 1818 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3 13.313.3
(D)
바인더
수지(D)
bookbinder
profit 		D-1D-1 3030 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4 4.44.4
(E)
용매(E)
menstruum 		E-1E-1 -- 2424 2424 -- 28.828.8 28.828.8 28.828.8
E-2E-2 -- 2424 -- 2424 14.414.4 14.414.4 14.414.4
E-3E-3 -- -- 2424 2424 -- -- --
E-4E-4 -- -- -- -- 4.84.8 -- --
E-5E-5 -- -- -- -- -- 4.84.8 --
E-6E-6 -- -- -- -- -- -- 4.84.8
(F)
첨가제(F)
additive 		F-1F-1 1010 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
상기 표 1 내지 3에서 사용된 각 성분은 다음과 같다.(A) 광중합성 화합물(A-1) 디펜타에리트리톨헥사아크릴레이트(DPHA, 제조사: 일본화약)Each ingredient used in Tables 1 to 3 above is as follows. (A) Photopolymerizable compound (A-1) Dipentaerythritol hexaacrylate (DPHA, manufacturer: Nippon Gunpowder)
(B) 광중합 개시제(B) Photopolymerization initiator
(B-1) 옥심계 개시제 (SPI-03, 제조사: 삼양)(B-1) Oxime-based initiator (SPI-03, manufacturer: Samyang)
(C) 착색제(C) Colorant
(C-1) 프탈로시아닌계 블루 안료 분산액 (B15:6, 제조사: SAKATA)(C-1) Phthalocyanine blue pigment dispersion (B15:6, manufacturer: SAKATA)
(C-2) 바이올렛 안료 분산액 (V23, 제조사: SAKATA)(C-2) Violet pigment dispersion (V23, manufacturer: SAKATA)
(D) 바인더 수지(D) Binder resin
(D-1) 산가 30~180 KOHmg/g, 및 중량평균분자량 5000 내지 20000 g/mol의 아크릴계 바인더 수지 (RY-100, 제조사: 쇼와덴코)(D-1) Acrylic binder resin with an acid value of 30 to 180 KOHmg/g and a weight average molecular weight of 5000 to 20000 g/mol (RY-100, manufacturer: Showa Denko)
(E) 용매(E) Solvent
(E-1) n-부틸 아세테이트 (n-BA, 비점: 126　°C ℃ @ 1 atm, 인화점:　　28.2　℃(by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-1) n-butyl acetate (n-BA, boiling point: 126°C ℃ @ 1 atm, flash point: 28.2°C (by tag closed test method), manufacturer: Sigma Aldrich)
(E-2) 프로필렌 글리콜 모노메틸 에테르 아세테이트 (PGMEA, 비점: 146.4 ℃ @ 1 atm, 인화점:　　47.7　℃ (by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-2) Propylene glycol monomethyl ether acetate (PGMEA, boiling point: 146.4 ℃ @ 1 atm, flash point: 47.7 ℃ (by tag closed test method), manufacturer: Sigma Aldrich)
(E-3) 디에틸렌 글리콜 메틸 에틸 에테르(MEDG, 비점: 176 ℃ @ 1 atm, 인화점:　68.5　℃ (by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-3) Diethylene glycol methyl ethyl ether (MEDG, boiling point: 176 ℃ @ 1 atm, flash point: 68.5 ℃ (by tag closed test method), manufacturer: Sigma Aldrich)
(E-4) 사이클로헥사논 (비점: 155.6 ℃ @ 1 atm, 인화점: 44 ℃ (by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-4) Cyclohexanone (boiling point: 155.6 ℃ @ 1 atm, flash point: 44 ℃ (by tag closed test method), manufacturer: Sigma Aldrich)
(E-5) N-사이클로헥실-2-피롤리돈 (비점: 284 ℃ @ 1 atm, 인화점:145　℃ (by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-5) N-Cyclohexyl-2-pyrrolidone (boiling point: 284 ℃ @ 1 atm, flash point: 145 ℃ (by tag closed test method), manufacturer: Sigma Aldrich)
(E-6) 3-메톡시부탄올 아세테이트 (비점: 171 ℃ @ 1 atm, 인화점:　62.5 ℃ (by 태크밀폐식 시험법), 제조사: 시그마 알드리치)(E-6) 3-methoxybutanol acetate (boiling point: 171 ℃ @ 1 atm, flash point: 62.5 ℃ (by Tac closed test method), manufacturer: Sigma Aldrich)
(F) 첨가제(F) Additives
(F-1) 불소계 계면활성제 (F-554, 제조사: DIC (10% 희석액 사용))(F-1) Fluorinated surfactant (F-554, manufacturer: DIC (using 10% dilution))
참고로, 상기 각 용매의 인화점은 ASTM D56 시험법에 따라 태크밀폐식 장비(Anton Paar社 TAG4)를 사용하여 측정할 수 있다.For reference, the flash point of each solvent can be measured using a tag-sealed equipment (Anton Paar TAG4) according to the ASTM D56 test method.
(평가)(evaluation)
평가예 1: 색 균일도 평가Evaluation Example 1: Color uniformity evaluation
실시예 1 내지 14 및 비교예 1 내지 6의 각 감광성　수지　조성물로부터, 패턴화된 감광성 수지막을 포함하는 컬러 필터 시편을 제조한 뒤, 감광성 수지막의 색 균일도를 평가하였다.Color filter specimens including a patterned photosensitive resin film were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the color uniformity of the photosensitive resin film was evaluated.
구체적으로, 스핀-코터(spin-coater, KDNS사의 K-Spin8)를 이용하여, 투명한 사각 유리기판(bare glass)에 감광성 수지 조성물을 각각 0.4 um의 두께로 도포하였다. 이후 가열판(hot-plate)을 이용하여 90 ℃에서 180초 동안 베이킹(baking)을 하고, 노광기(Nikon사의 I10C)를 이용하여 500 mJ의 출력(power)으로 노광한 후, 230 ℃의 가열판(hot-plate)에서 5분 동안 베이킹(baking)하여, 감광성 수지막을 포함하는 컬러 필터 시편 두께: 4000 Å, 가로*세로= 2cm*2cm)을 제조하였다. Specifically, the photosensitive resin composition was applied to a transparent square glass substrate (bare glass) to a thickness of 0.4 um using a spin-coater (K-Spin8 from KDNS). Afterwards, baking was performed at 90°C for 180 seconds using a hot-plate, exposure was performed using an exposure machine (Nikon's I10C) at a power of 500 mJ, and then baking was performed using a hot-plate at 230°C. -plate) for 5 minutes to prepare a color filter specimen including a photosensitive resin film (thickness: 4000 Å, width*length=2cm*2cm).
광학 현미경(기기명: MX61, 제조사: OLYMPUS) 기기를 이용하여 (투과 모드) 하에 컬러 필터 시편의 이미지를 측정한 뒤 저장하고, Microscope Color 균일도 프로그램을 이용하여 그래프를 얻고, Color 균일도 그래프로부터 L이 -20% 내지 5%인 구간에서의 Pixel 수의 합(적분값, 단위: ea)을 구하여, 색 균일도의 수준을 파악하였다. 그 결과는 하기 표 4 내지 6에 기재하였다.Measure and save the image of the color filter specimen under (transmission mode) using an optical microscope (device name: MX61, manufacturer: OLYMPUS), obtain a graph using the Microscope Color Uniformity program, and from the color uniformity graph, L is - The level of color uniformity was determined by calculating the sum (integral value, unit: ea) of the number of pixels in the section from 20% to 5%. The results are shown in Tables 4 to 6 below.
참고로, 감광성 수지막의 Color 균일도 그래프에서 L이 -20% 내지 5%인 구간에서의 Pixel 수의 합(적분값, 단위: ea)이 적을수록, 감광성 수지막의 색이 균일하다.For reference, in the color uniformity graph of the photosensitive resin film, the smaller the sum (integral value, unit: ea) of the number of pixels in the section where L is -20% to 5%, the more uniform the color of the photosensitive resin film.
평가예 2: 두께 균일도 평가Evaluation Example 2: Thickness uniformity evaluation
실시예 1 내지 14 및 비교예 1 내지 6의 각 감광성　수지　조성물로부터, 감광성 수지막을 포함하는 컬러 필터 시편을 제조한 뒤, 감광성 수지막의 두께 균일도를 평가하였다.Color filter specimens containing a photosensitive resin film were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the thickness uniformity of the photosensitive resin film was evaluated.
구체적으로, 평가예 1과 동일한 방법으로 컬러 필터 시편을 제조한 뒤, ST-5000(K-MAC)을 이용하여, 감광성 수지막의 최대 두께와 최소 두께의 차이(TMax-TMin)을 측정하여, 두께 균일도의 수준을 파악하였다. 그 결과는 하기 표 4 내지 6에 나타내었다.Specifically, after manufacturing a color filter specimen in the same manner as Evaluation Example 1, the difference between the maximum and minimum thickness of the photosensitive resin film (T Max -T Min ) was measured using ST-5000 (K-MAC). , the level of thickness uniformity was determined. The results are shown in Tables 4 to 6 below.
참고로, 감광성 수지막의 최대 두께와 최소 두께의 차이(TMax-TMin)가 작을수록, 감광성 수지막의 두께가 균일하다.For reference, the smaller the difference (T Max -T Min ) between the maximum and minimum thickness of the photosensitive resin film, the more uniform the thickness of the photosensitive resin film.
평가예 3: 사선 불량 평가Evaluation example 3: Evaluation of diagonal defects
실시예 1 내지 14 및 비교예 1 내지 6의 각 감광성　수지　조성물로부터 감광성 수지막을 포함하는 컬러 필터 시편을 제조한 뒤, 감광성 수지막의 사선 불량을 평가하였다.Color filter specimens including photosensitive resin films were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the diagonal defects of the photosensitive resin films were evaluated.
구체적으로, 평가예 1과 동일한 방법으로 컬러 필터 시편을 제조한 뒤, 광학현미경을 통해 감광성 수지막을 위에서 바라본 사진을 찍어, 사선 불량 여부를 O(양호), △(불량 일부 존재), X(불량)으로 평가하였다. 그 결과는 하기 표 4 내지 6에 나타내었다.Specifically, after manufacturing a color filter specimen in the same manner as Evaluation Example 1, a photo of the photosensitive resin film viewed from above was taken through an optical microscope, and the presence of diagonal defects was graded as O (good), △ (some defects exist), and ) was evaluated. The results are shown in Tables 4 to 6 below.
평가예 4: 이물 면적 평가Evaluation Example 4: Foreign matter area evaluation
실시예 1 내지 14 및 비교예 1 내지 6의 각 감광성　수지　조성물로부터, 감광성 수지막을 포함하는 컬러 필터 시편을 제조한 뒤, 패턴화된 감광성 수지막 내 이물 면적을 평가하였다.Color filter specimens including photosensitive resin films were prepared from each of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 6, and then the area of foreign matter in the patterned photosensitive resin film was evaluated.
구체적으로, 평가예 1과 동일한 방법으로 컬러 필터 시편을 제조한 뒤, CDSEM(HITACHI)을 통해 감광성 수지막을 위에서 바라본 사진을 찍어, 감광성 수지막의 총 면적(100 sq%) 당 이물의 면적을 확인하고, 그 결과를 하기 표 4 내지 6에 나타내었다.Specifically, after manufacturing a color filter specimen in the same manner as Evaluation Example 1, a photo of the photosensitive resin film viewed from above was taken using CDSEM (HITACHI), the area of foreign matter per total area (100 sq%) of the photosensitive resin film was confirmed, and , the results are shown in Tables 4 to 6 below.
감광성 수지 조성물 내 용매의 중량비Weight ratio of solvent in photosensitive resin composition 컬러 필터 시편의 평가Evaluation of color filter specimens
E-1E-1 E-2E-2 E-3E-3 E-4E-4 E-5E-5 E-6E-6 색 균일도 (ea)Color uniformity (ea) 두께 균일도 (Å)Thickness Uniformity (Å) 사선 불량Bad diagonal line 이물 면적 (sq%)Foreign matter area (sq%)
실시예
1Example
One 		1010 8080 1010 -- -- -- 12851285 3131 OO 2.82.8
실시예2Example 2 2020 7070 1010 -- -- -- 12811281 2929 OO 2.72.7
실시예3Example 3 3030 6060 1010 -- -- -- 12771277 3030 OO 2.82.8
실시예4Example 4 4040 5050 1010 -- -- -- 12671267 2828 OO 2.62.6
실시예5Example 5 5050 4040 1010 -- -- -- 12401240 2727 OO 2.42.4
실시예6Example 6 6060 3030 1010 -- -- -- 11531153 2424 OO 2.12.1
실시예7Example 7 7070 2020 1010 -- -- -- 11501150 2323 OO 2.02.0
실시예8Example 8 8080 1010 1010 -- -- -- 11481148 2222 OO 1.81.8
감광성 수지 조성물 내 용매의 중량비Weight ratio of solvent in photosensitive resin composition 컬러 필터 시편의 평가Evaluation of color filter specimens
E-1E-1 E-2E-2 E-3E-3 E-4E-4 E-5E-5 E-6E-6 색 균일도 (ea)Color uniformity (ea) 두께 균일도 (Å)Thickness Uniformity (Å) 사선 불량Bad diagonal line 이물 면적 (sq%)Foreign matter area (sq%)
실시예
9Example
9 		6969 3030 1One -- -- -- 11471147 2222 OO 1.81.8
실시예10Example 10 6565 3030 55 -- -- -- 11511151 2323 OO 2.02.0
실시예6Example 6 6060 3030 1010 -- -- -- 11531153 2424 OO 2.12.1
실시예11Example 11 5555 3030 1515 -- -- -- 11541154 2424 OO 2.22.2
실시예12Example 12 5050 3030 2020 -- -- -- 12211221 2727 OO 2.52.5
실시예13Example 13 4545 3030 2525 -- -- -- 12351235 2828 OO 2.62.6
실시예14Example 14 4040 3030 3030 -- -- -- 12411241 2929 OO 2.72.7
감광성 수지 조성물 내 용매의 중량비Weight ratio of solvent in photosensitive resin composition 컬러 필터 시편의 평가Evaluation of color filter specimens
E-1E-1 E-2E-2 E-3E-3 E-4E-4 E-5E-5 E-6E-6 색 균일도 (ea)Color uniformity (ea) 두께 균일도 (Å)Thickness Uniformity (Å) 사선 불량Bad diagonal line 이물 면적 (sq%)Foreign matter area (sq%)
비교예
1Comparative example
One 		5050 5050 -- -- -- -- 14511451 197197 XX 1414
비교예2Comparative example 2 5050 -- 5050 -- -- -- 13121312 3535 △△ 66
비교예3Comparative Example 3 -- 5050 5050 -- -- -- 14111411 135135 △△ 1212
비교예4Comparative example 4 6060 3030 -- 1010 -- -- 14561456 193193 XX 1313
비교예5Comparative Example 5 6060 3030 -- -- 1010 -- 15311531 201201 XX 1717
비교예6Comparative Example 6 6060 3030 -- -- -- 1010 13331333 3636 △△ 77
표 4 내지 6에 따르면, 실시예 1 내지 14의 각 감광성 수지 조성물을 이용하여 제조된 컬러 필터 시편은, 감광성 수지막의 색 및 두께가 균일하면서 사선 불량 및 이물이 억제된 것을 알 수 있다. 구체적으로, 인화점이 40 ℃ 미만인 제1 용매, 인화점이 40 ℃ 이상 내지 60 ℃ 미만인 제2 용매, 및 인화점이 60 ℃ 이상인 제3 용매 중 2종만 혼합한 경우(비교예 1 내지 3), 감광성 수지막의 색 및 두께가 균일하지 못하거나 사선 불량 및 이물이 발생한다.상기 제2 용매 2종과 상기 제3 용매 1종을 혼합하는 것처럼, 일 구현예와 다르게 혼합하는 경우에도(비교예 4 내지 6), 감광성 수지막의 색 및 두께가 균일하지 못하거나 사선 불량 및 이물이 발생한다.According to Tables 4 to 6, it can be seen that the color filter specimens manufactured using each of the photosensitive resin compositions of Examples 1 to 14 had uniform color and thickness of the photosensitive resin film while suppressing diagonal defects and foreign matter. Specifically, when only two of the first solvent with a flash point of less than 40 ℃, the second solvent with a flash point of 40 ℃ or more to less than 60 ℃, and the third solvent with a flash point of 60 ℃ or more are mixed (Comparative Examples 1 to 3), the photosensitive resin The color and thickness of the film are not uniform, or diagonal defects and foreign matter occur. Even when mixed differently from one embodiment, such as mixing the two types of second solvent and one type of third solvent, (Comparative Examples 4 to 6 ), the color and thickness of the photosensitive resin film is not uniform, or diagonal defects and foreign substances occur.
그러나, 일 구현예와 같이 상기 제1 용매, 상기 제2 용매 및 상기 제3 용매를 각각 적어도 1종씩 사용하는 경우(실시예 1 내지 14), 감광성 수지막의 색 및 두께가 균일하면서 사선 불량 및 이물이 억제된다.However, when at least one type of each of the first solvent, the second solvent, and the third solvent is used as in one embodiment (Examples 1 to 14), the color and thickness of the photosensitive resin film are uniform, while diagonal defects and foreign matter are eliminated. This is suppressed.
특히, 실시예 1 내지 14 중에서도, 상기 제1 내지 제3 용매의 함량이 하기 수학식 1을 만족하고; 상기 제1 용매의 함량은 55 중량부 이상 내지 80 중량부 이하에 가까울수록; 상기 제2 용매의 함량은 10 중량부 이상 내지 30 중량부 이하에 가까울수록; 상기 제3 용매는 1 중량부 이상 내지 30 중량부 이하에 가까울수록 상기 제1 내지 제3 용매에 의한 시너지 효과가 향상될 수 있다.In particular, among Examples 1 to 14, the content of the first to third solvents satisfies Equation 1 below; The closer the content of the first solvent is to 55 parts by weight or more to 80 parts by weight or less; The closer the content of the second solvent is to 10 parts by weight or more to 30 parts by weight or less; The synergy effect of the first to third solvents may be improved as the amount of the third solvent increases from 1 part by weight to 30 parts by weight.
[수학식 1][Equation 1]
M1 > (M2+M3)M1 > (M2+M3)
상기 수학식 1에서, M1은 상기 제1 용매의 중량이고, M2는 제2 용매의 중량이고, M3는 상기 제3 용매의 중량이다.In Equation 1, M1 is the weight of the first solvent, M2 is the weight of the second solvent, and M3 is the weight of the third solvent.
이상 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고, 특허청구범위와 발명의 상세한 설명 및 첨부한 도면의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고, 이 또한 본 발명의 범위에 속하는 것은 당연하다.Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and this also applies to the present invention. It is natural that it falls within the scope of the invention.

Claims (20)

  1. (A) 광중합성 화합물;(A) Photopolymerizable compound;
    (B) 광중합 개시제;(B) photopolymerization initiator;
    (C) 착색제;(C) colorant;
    (D) 바인더 수지; 및(D) binder resin; and
    (E) 용매(E) Solvent
    를 포함하고,Including,
    상기 용매는 제1 용매 내지 제3 용매를 포함하고,The solvent includes first to third solvents,
    제1 용매는 인화점이 40 ℃ 미만이고, The first solvent has a flash point below 40°C,
    제2 용매는 인화점이 40 ℃ 이상 내지 60 ℃ 미만이고,The second solvent has a flash point of 40°C or more and less than 60°C,
    제3 용매는 인화점이 60 ℃ 이상인,The third solvent has a flash point of 60 ℃ or higher,
    감광성 수지 조성물.Photosensitive resin composition.
  2. 제1항에 있어서,According to paragraph 1,
    상기 제1 용매, 상기 제2 용매 및 상기 제3 용매는 하기 수학식 1을 만족하는 감광성 수지 조성물:A photosensitive resin composition in which the first solvent, the second solvent, and the third solvent satisfy the following equation 1:
    [수학식 1][Equation 1]
    M1 > (M2+M3)M1 > (M2+M3)
    상기 수학식 1에서,In Equation 1 above,
    M1은 상기 제1 용매의 중량이고,M1 is the weight of the first solvent,
    M2는 상기 제2 용매의 중량이고,M2 is the weight of the second solvent,
    M3는 상기 제3 용매의 중량이다.M3 is the weight of the third solvent.
  3. 제1항에 있어서,According to paragraph 1,
    상기 용매의 총 중량 100 중량부 중에서, 상기 제1 용매는 40 중량부 이상 내지 80 중량부 이하로 포함되고, 상기 제2 용매는 1 중량부 이상 내지 50 중량부 이하로 포함되고, 상기 제3 용매는 0.1 중량부 이상 내지 40 중량부 이하로 포함되는 감광성 수지 조성물.Of the total weight of 100 parts by weight of the solvent, the first solvent is contained in an amount of 40 parts by weight or more and 80 parts by weight or less, the second solvent is contained in an amount of 1 part by weight or more and 50 parts by weight or less, and the third solvent A photosensitive resin composition contained in an amount of 0.1 parts by weight or more and 40 parts by weight or less.
  4. 제1항에 있어서,According to paragraph 1,
    상기 제1 용매는 1 atm 하에서 비점이 110 ℃ 이상 내지 140 ℃ 미만인 감광성 수지 조성물.The first solvent is a photosensitive resin composition having a boiling point of 110°C or more and less than 140°C under 1 atm.
  5. 제1항에 있어서,According to paragraph 1,
    상기 제1 용매는 아세테이트 제1 용매 또는 알코올계 제1 용매인 감광성 수지 조성물.The photosensitive resin composition wherein the first solvent is an acetate first solvent or an alcohol-based first solvent.
  6. 제1항에 있어서,According to paragraph 1,
    상기 제1 용매는 n-부틸 아세테이트(n-butyl acetate, n-BA)인 감광성 수지 조성물.The photosensitive resin composition wherein the first solvent is n-butyl acetate (n-BA).
  7. 제1항에 있어서,According to paragraph 1,
    상기 제1 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하로 포함되는 감광성 수지 조성물.The photosensitive resin composition wherein the first solvent is included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
  8. 제1항에 있어서,According to paragraph 1,
    상기 제2 용매는 1 atm 하에서 비점이 125 ℃ 이상 내지 150 ℃ 미만인 감광성 수지 조성물.The second solvent is a photosensitive resin composition having a boiling point of 125°C or more and less than 150°C under 1 atm.
  9. 제1항에 있어서,According to paragraph 1,
    상기 제2 용매는 아세테이트계 제2 용매인 감광성 수지 조성물.The photosensitive resin composition wherein the second solvent is an acetate-based second solvent.
  10. 제1항에 있어서,According to paragraph 1,
    상기 제2 용매는 프로필렌 글리콜 모노메틸 에테르 아세테이트(propylene glycol monomethyl ether acetate, PGMEA), 에틸렌글리콜 모노 메틸 에테르 아세테이트(Ethylene glycol monomethyl ether acetate, EGMEA), 또는 이들의 조합인 감광성 수지 조성물.The second solvent is a photosensitive resin composition that is propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate (EGMEA), or a combination thereof.
  11. 제1항에 있어서,According to paragraph 1,
    상기 제2 용매는 상기 감광성 수지 조성물 100 중량% 중 1 중량% 이상 내지 50 중량% 이하로 포함되는 감광성 수지 조성물.The photosensitive resin composition wherein the second solvent is included in an amount of 1% by weight or more and 50% by weight or less based on 100% by weight of the photosensitive resin composition.
  12. 제1항에 있어서,According to paragraph 1,
    상기 제3 용매는 1 atm 하에서 비점이 150 ℃ 이상인 감광성 수지 조성물.The third solvent is a photosensitive resin composition having a boiling point of 150° C. or higher at 1 atm.
  13. 제1항에 있어서,According to paragraph 1,
    상기 제3 용매는 2개 이상의 에테르기를 포함하는 구조를 가지는 감광성 수지 조성물.The third solvent is a photosensitive resin composition having a structure containing two or more ether groups.
  14. 제1항에 있어서,According to paragraph 1,
    상기 제3 용매는 디에틸렌 글리콜 메틸 에틸 에테르(diethylene glycol methyl ethyl ether, MEDG)인 감광성 수지 조성물.The photosensitive resin composition wherein the third solvent is diethylene glycol methyl ethyl ether (MEDG).
  15. 제1항에 있어서,According to paragraph 1,
    상기 제3 용매는 상기 감광성 수지 조성물 100 중량% 중 0.1 중량% 이상 내지 25 중량% 이하로 포함되는 감광성 수지 조성물.The third solvent is included in an amount of 0.1% by weight or more and 25% by weight or less based on 100% by weight of the photosensitive resin composition.
  16. 제1항에 있어서,According to paragraph 1,
    상기 착색제는 안료를 포함하고, 상기 안료는 청색 안료, 자색 안료 또는 이들의 혼합물을 포함하는 감광성 수지 조성물.A photosensitive resin composition wherein the colorant includes a pigment, and the pigment includes a blue pigment, a purple pigment, or a mixture thereof.
  17. 제1항에 있어서,According to paragraph 1,
    상기 감광성 수지 조성물은, 상기 감광성 수지 조성물 총량에 대해,The photosensitive resin composition is, with respect to the total amount of the photosensitive resin composition,
    상기 (A) 광중합성 화합물 0.1 중량% 내지 20 중량%;(A) 0.1% to 20% by weight of the photopolymerizable compound;
    상기 (B) 광중합 개시제 0.1 중량% 내지 5 중량%;(B) 0.1% to 5% by weight of photopolymerization initiator;
    상기 (C) 착색제 5 중량% 내지 50 중량%;5% to 50% by weight of the (C) colorant;
    상기 (D) 바인더 수지 0.1 중량% 내지 20 중량%; 및0.1% to 20% by weight of the (D) binder resin; and
    상기 (E) 용매 잔부량(E) Solvent remaining amount
    을 포함하는 감광성 수지 조성물.A photosensitive resin composition containing a.
  18. 제1항 내지 제17항 중 어느 한 항의 감광성 수지 조성물을 이용하여 제조된 감광성 수지막.A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 17.
  19. 제18항의 감광성 수지막을 포함하는 컬러 필터.A color filter comprising the photosensitive resin film of claim 18.
  20. 제19항의 컬러 필터를 포함하는 CMOS 이미지 센서.A CMOS image sensor including the color filter of claim 19.
PCT/KR2023/005392 2022-09-15 2023-04-20 Photosensitive resin composition, photosensitive resin film manufactured using same, and color filter WO2024058334A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020220116664A KR20240037760A (en) 2022-09-15 2022-09-15 Photosensitive resin composition, photosensitive resin layer using the same and color filter
KR10-2022-0116664 2022-09-15

Publications (1)

Publication Number Publication Date
WO2024058334A1 true WO2024058334A1 (en) 2024-03-21

Family

ID=90275450

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/005392 WO2024058334A1 (en) 2022-09-15 2023-04-20 Photosensitive resin composition, photosensitive resin film manufactured using same, and color filter

Country Status (2)

Country Link
KR (1) KR20240037760A (en)
WO (1) WO2024058334A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090140220A1 (en) * 2007-11-30 2009-06-04 Cheil Industries Inc. Photosensitive Resin Composition for Color Filter and Color Filter Using Same
KR20100051395A (en) * 2008-11-07 2010-05-17 주식회사 엘지화학 Photoresist resin composition and the liquid crystal display comprising micropattern thereof
KR20190027931A (en) * 2016-08-29 2019-03-15 후지필름 가부시키가이샤 Composition, film, near-IR cut filter, pattern forming method, laminate, solid-state image sensor, image display device, camera module and infrared sensor
KR20190044556A (en) * 2017-10-20 2019-04-30 동우 화인켐 주식회사 A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter
KR20190049505A (en) * 2017-10-31 2019-05-09 사카타 인쿠스 가부시키가이샤 Black pigment dispersion composition and black pigment dispersion resist composition containing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090140220A1 (en) * 2007-11-30 2009-06-04 Cheil Industries Inc. Photosensitive Resin Composition for Color Filter and Color Filter Using Same
KR20100051395A (en) * 2008-11-07 2010-05-17 주식회사 엘지화학 Photoresist resin composition and the liquid crystal display comprising micropattern thereof
KR20190027931A (en) * 2016-08-29 2019-03-15 후지필름 가부시키가이샤 Composition, film, near-IR cut filter, pattern forming method, laminate, solid-state image sensor, image display device, camera module and infrared sensor
KR20190044556A (en) * 2017-10-20 2019-04-30 동우 화인켐 주식회사 A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter
KR20190049505A (en) * 2017-10-31 2019-05-09 사카타 인쿠스 가부시키가이샤 Black pigment dispersion composition and black pigment dispersion resist composition containing the same

Also Published As

Publication number Publication date
KR20240037760A (en) 2024-03-22

Similar Documents

Publication Publication Date Title
WO2019083112A1 (en) Composition comprising quantum dots, method for preparing quantum dots, and color filter
WO2013094828A1 (en) Photosensitive resin composition and color filter using the same
WO2011002247A2 (en) 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
WO2015005546A1 (en) Black photosensitive resin composition and light blocking layer using same
WO2012091224A1 (en) Photosensitive resin composition for color filter and color filter using same
WO2015122567A1 (en) Novel dye compound, photosensitive resin composition comprising same, and colour filter
WO2013100276A1 (en) Photosensitive resin composition for color filter and color filter using the same
WO2020022670A1 (en) Binder resin, photosensitive resin composition, photoresist, color filter, and display device
WO2020218709A1 (en) Curable composition containing quantum dots, and resin film and display device using same
WO2024058334A1 (en) Photosensitive resin composition, photosensitive resin film manufactured using same, and color filter
WO2019164157A1 (en) Compound, colorant composition comprising same, and resin composition comprising same
WO2019107687A1 (en) Colorant composition, colorant dispersion, photosensitive resin composition, color filter and liquid crystal display
WO2023200045A1 (en) Photosensitive resin composition, photosensitive resin layer prepared using same, and color filter
WO2021210783A1 (en) Photosensitive resin composition, and photosensitive resin film and color filter manufactured by using same
WO2024048894A1 (en) Photosensitive resin composition, photosensitive resin layer using the same and color filter
WO2021187853A1 (en) Photosensitive resin composition, photosensitive resin film prepared using same, and display device
WO2024043429A1 (en) Photosensitive resin composition, photosensitive resin layer manufactured using same, and color filter
WO2024048893A1 (en) Photosensitive resin composition, photosensitive resin layer manufactured using same, and color filter
WO2015108240A1 (en) Photosensitive resin composition for color filter and color filter using same
WO2020218676A1 (en) Light-shielding barrier rib composition, light-shielding barrier rib manufactured using same, and display device
KR101288559B1 (en) Photosensitive resin composition and color filter using same
WO2022182157A1 (en) Photosensitive resin composition for forming partition walls, partition wall structure manufactured using same, and display device comprising partition walls
WO2024085390A1 (en) Method for manufacturing pixel definition layer
WO2024085388A1 (en) Method for manufacturing pixel-defining layer
WO2024085389A1 (en) Method for manufacturing pixel-defining layer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23865642

Country of ref document: EP

Kind code of ref document: A1