WO2022145795A1 - Negative photo-sensitive resin composition with low-temperature curability and low refractive index - Google Patents

Negative photo-sensitive resin composition with low-temperature curability and low refractive index Download PDF

Info

Publication number
WO2022145795A1
WO2022145795A1 PCT/KR2021/018681 KR2021018681W WO2022145795A1 WO 2022145795 A1 WO2022145795 A1 WO 2022145795A1 KR 2021018681 W KR2021018681 W KR 2021018681W WO 2022145795 A1 WO2022145795 A1 WO 2022145795A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
formula
unsaturated compound
resin composition
Prior art date
Application number
PCT/KR2021/018681
Other languages
French (fr)
Korean (ko)
Inventor
정종호
윤혁민
김진선
전승한
김의순
류영준
안창환
Original Assignee
주식회사 동진쎄미켐
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 주식회사 동진쎄미켐 filed Critical 주식회사 동진쎄미켐
Priority to CN202180086312.7A priority Critical patent/CN116648671A/en
Publication of WO2022145795A1 publication Critical patent/WO2022145795A1/en

Links

Classifications

    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/18—Esters containing halogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a negative photosensitive resin composition capable of being cured at a low temperature of 150° C. or less and having a low refractive index, and a display device including a cured product thereof.
  • the luminance increase rate is changed according to the refractive index of the resin constituting the prism structure.
  • the luminance increase rate is changed according to the refractive index of the resin constituting the prism structure.
  • light loss occurs due to a difference in refractive index of materials located in the upper and lower layers.
  • the photosensitive resin used as an interlayer insulating film and flattening of a color filter in a flexible display that has been given flexibility to fold and unfold by replacing the glass substrate used in the existing LCD and OLED with a plastic film is processed at low temperature.
  • a photosensitive resin composition that can be cured in
  • Another object of the present invention is to provide a display device including a cured product of the photosensitive resin composition.
  • the negative photosensitive resin composition includes a repeating unit derived from a first unsaturated compound containing a thermosetting functional group and a repeating unit derived from a second unsaturated compound containing fluorine.
  • a repeating unit derived from a first unsaturated compound containing a thermosetting functional group and a repeating unit derived from a second unsaturated compound containing fluorine.
  • an acrylic copolymer, a photoinitiator and a solvent included in order to solve the above problems.
  • the acrylic copolymer may include 5 to 30% by weight of each of the repeating units derived from the first and second unsaturated compounds.
  • the acrylic copolymer may include 10 to 30% by weight of the repeating unit derived from the first unsaturated compound and 5 to 30% by weight of the repeating unit derived from the second unsaturated compound.
  • the acrylic copolymer may further include a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, and specifically may be included in an amount of 1 to 50% by weight.
  • the acrylic copolymer may include 5 to 30 wt% of the repeating unit derived from the first and second unsaturated compounds, respectively, and 1 to 50 wt% of the repeating unit derived from the olefinically unsaturated compound.
  • the first unsaturated compound may include a linear or branched aliphatic structure having an epoxy group or an alicyclic structure having an epoxy group.
  • the first unsaturated compound may include one or more structures selected from the group consisting of Chemical Formulas 1 to 3 below.
  • n is an integer of 1 to 10
  • R in Formula 3 is an organic group having at least one of an alkyl, alkene, and allyl structure having 0 to 10 carbon atoms.
  • the second unsaturated compound may include one or more structures selected from the group consisting of Chemical Formulas 4 to 6 below.
  • n is an integer of 0 to 9
  • n is an integer of 1 to 10
  • n is an integer of 0 to 9.
  • the weight average molecular weight (Mw) of the acrylic copolymer may be 1,000 to 10,000.
  • the photoinitiator may be included in the photosensitive resin composition in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the negative photosensitive resin composition may further include an ethylenically unsaturated urethane oligomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the ethylenically unsaturated urethane oligomer may contain one or more fluorine atoms.
  • the negative photosensitive resin composition may further include an ethylenically unsaturated polyfunctional monomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the ethylenically unsaturated polyfunctional monomer may include fluorine.
  • the solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the acrylic copolymer, for example, the solvent is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol.
  • a display device includes a cured product of the negative photosensitive resin composition.
  • the display device may include an optical member having a refractive index of 1.5 or less, and the optical member may include the curing body.
  • the photosensitive resin composition of the present invention can be cured at 150° C. or less, so it is possible to form a pattern by a photoresist process even at low temperatures, and a refractive index of 1.50 or less is possible, so as a display material, light loss due to interlayer refractive index is reduced and panel brightness is increased This has the effect of increasing battery life by suppressing it.
  • the negative photosensitive resin composition according to an embodiment of the present invention is a repeating unit derived from a first unsaturated compound containing a thermosetting functional group in order to have low refractive properties while being curable at 150° C. or less, and a second unsaturated compound containing fluorine It contains an acrylic copolymer including a repeating unit derived from, a photoinitiator, and a solvent capable of dissolving the composition.
  • the acrylic copolymer serves to facilitate the formation of a pattern without scum occurring in the process of developing the photosensitive resin composition.
  • the acrylic copolymer may include 5 to 30% by weight of the repeating unit derived from the first unsaturated compound, specifically 10 to 30% by weight.
  • the amount of the repeating unit derived from the first unsaturated compound is less than 5% by weight, the thermal crosslinking property of the composition is deteriorated, so that the adhesive strength of the cured film of the composition may be weakened, and when it exceeds 30% by weight, the above
  • the resolution of a display product using a film in which the composition is cured is lowered, and there may be problems in which the stability of the composition is lowered.
  • the acrylic copolymer may include 5 to 30% by weight of the repeating unit derived from the second unsaturated compound. If the amount of the repeating unit derived from the second unsaturated compound is less than 5% by weight, a problem may occur that the refractive index of the composition becomes higher than 1.50, and if it exceeds 30% by weight, cloudiness may occur in the process of developing the composition. In addition, there may be a problem of gelation during the copolymerization reaction.
  • the acrylic copolymer may further include repeating units derived from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or mixtures thereof as well as repeating units derived from the first and second unsaturated compounds.
  • the repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is included in the acrylic copolymer to provide an effect of improving the solubility of the photosensitive resin composition in an aqueous alkali solution.
  • the repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof may be included in the acrylic copolymer in an amount of 1 to 50 wt%, more specifically 5 to 40 wt%.
  • the repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is included in the acrylic copolymer in an amount of less than 1% by weight, it may be difficult to dissolve in an aqueous alkali solution as a developer of the photosensitive resin composition. And, when it is included in more than 50% by weight, the solubility of the photosensitive resin composition in an aqueous alkali solution, which is a developer, may be excessively increased.
  • the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride may be, for example, one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and anhydrides of these unsaturated dicarboxylic acids, and the unsaturated carboxylic acid Or an unsaturated carboxylic acid anhydride may be used individually, and 2 or more types may be mixed and used for it.
  • acrylic acid, methacrylic acid, or maleic anhydride is good in terms of copolymerization reactivity and solubility in aqueous alkali solution as a developer.
  • the acrylic copolymer may further include a repeating unit derived from an olefinically unsaturated compound.
  • the olefin-based unsaturated compound is included in the acrylic copolymer to improve transparency of the cured product of the acrylic copolymer, thereby further increasing the resolution of a display device in the future.
  • the repeating unit derived from the olefin unsaturated compound may be included in the acrylic copolymer in an amount of 1 to 50 wt%.
  • the repeating unit derived from the olefinically unsaturated compound is included in the acrylic copolymer in an amount of less than 1% by weight, when the film in which the photosensitive resin composition is cured is used in a display device, a problem of lowering the resolution of the display device may occur. In addition, a problem of poor heat resistance of the film may also occur.
  • the repeating unit derived from the olefinically unsaturated compound is included in the acrylic copolymer in an amount of more than 50% by weight, it may be difficult to dissolve the acrylic copolymer in an aqueous alkali solution as a developer.
  • olefinically unsaturated compound examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl Methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1 -Adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboronyl Acrylate, phenyl methacrylate,
  • the first unsaturated compound may specifically include an epoxy group as a thermosetting functional group. More specifically, for example, oxane, tetrahydrofuran (THF), etc. may be included, but is not limited thereto.
  • an epoxy group as a thermosetting functional group. More specifically, for example, oxane, tetrahydrofuran (THF), etc. may be included, but is not limited thereto.
  • the first unsaturated compound preferably includes a linear or branched aliphatic structure having an epoxy group or an alicyclic structure having an epoxy group, and preferably does not include an aromatic ring. In the case of having an aromatic ring, a problem of increasing the refractive index may occur.
  • the first unsaturated compound may specifically include one epoxy group, and when there are two or more epoxy groups, a problem in that the acrylic copolymer is gelled may occur.
  • the first unsaturated compound may include one or more structures selected from the group consisting of more specifically the following Chemical Formulas 1 to 3, but is not limited to the following Chemical Formulas 1 to 3 structures, and the following Chemical Formulas 1 to 3 structures In the alicyclic hydrocarbon moiety may be replaced by an aliphatic. However, in the case of a structure in which an alicyclic hydrocarbon portion is substituted with an aromatic hydrocarbon in the structures of Chemical Formulas 1 to 3, there may be a problem in that the composition does not exhibit low refractive properties.
  • n is an integer of 1 to 10, preferably an integer of 1 to 5
  • R in Formula 3 is an organic group having at least one of an alkyl, alkene, and allyl structure having 0 to 10 carbon atoms.
  • n in Formula 2 is 1 to 5
  • the resolution of the film in which the photosensitive resin composition is cured is advantageous, but is not limited to n.
  • the second unsaturated compound may have a structure including 1 to 2 acrylate groups together with fluorine.
  • the fluorine is included in the acrylic copolymer to significantly lower the refractive index of the photosensitive resin composition.
  • the first unsaturated compound may be excessively polymerized with the second unsaturated compound, so that fluorine in the second unsaturated compound may serve to lower the refractive index, but the pattern (resolution) characteristics may be poor. Vulnerability can be a problem.
  • the second unsaturated compound may include, for example, one or more structures selected from the group consisting of Chemical Formulas 4 to 6 below. However, it is not limited to the following structure.
  • n is an integer of 0 to 9
  • n is an integer of 1 to 10
  • n is an integer of 0 to 9.
  • the second unsaturated compound may help to form a pattern of the photosensitive resin composition and set the refractive index of the photosensitive resin composition to 1.5 or less.
  • the acrylic copolymer may have a weight average molecular weight (Mw), specifically, a polystyrene equivalent weight average molecular weight (Mw) of 1,000 to 10,000.
  • Mw weight average molecular weight
  • Mw polystyrene equivalent weight average molecular weight
  • the weight average molecular weight (Mw) is less than 1,000, the developability and the remaining film rate of the photosensitive resin composition may be deteriorated, and pattern development and heat resistance may be deteriorated.
  • the weight average molecular weight (Mw) exceeds 10,000, a problem of poor pattern developability may occur.
  • the photoinitiator is preferably included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the photoinitiator is included in an amount of less than 0.1 parts by weight, there may be a problem that the residual film ratio is deteriorated due to low sensitivity, and when it exceeds 30 parts by weight, developability is deteriorated, and the resolution of the cured product of the photosensitive resin composition is lowered. can occur
  • the photoinitiator may specifically include a radical photoinitiator, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaninoacetophenone, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morph Polynopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl Acetophenone compounds such as ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl
  • Triazine-based chemicals 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-phenylpropane-1- One, 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenyl) Sulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate; 1-(4-pheny
  • the photoinitiator may include at least one ion photoinitiator together with the radical photoinitiator in order to improve chemical resistance and adhesion of the photosensitive composition in a low temperature process.
  • the ion photoinitiator may be a cationic photoinitiator, an anionic photoinitiator, or a mixture thereof, for example, phenyl (4-methoxyphenyl) iodonium hexafluoride, N,N-dimethyl-N-benzyltrifluoromethanesulfonic acid, 4-methylphenyl (4- (2-methylpropylphenyl)) iodonium hexafluoride, and phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride can be used, and one or more of these can be mixed and used as needed. It is not limited to an example.
  • the ionic photoinitiator is preferably
  • the photosensitive resin composition may further include an ethylenically unsaturated urethane oligomer to secure low refractive properties.
  • the ethylenically unsaturated urethane oligomer is preferably included in an amount of 1 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content of the ethylenically unsaturated urethane oligomer is less than 1 part by weight, it may be difficult to secure the low refractive properties of the photosensitive resin composition and a problem that the remaining film ratio is deteriorated may occur. problems may arise.
  • the ethylenically unsaturated urethane oligomer has 2 to 10 functional groups, more specifically 2 to 6 functional groups, and may have a structure that does not include an aromatic structure.
  • the ethylenically unsaturated urethane oligomer has at least two functional groups to have an effect of improving the film curing degree upon photocuring in the photosensitive resin composition, and when the functional group is 11 or more, a problem of lowering resolution may occur, In the case of 6 or less, the effect of improving adhesion and resolution may be particularly excellent.
  • the ethylenically unsaturated urethane oligomer may also contain one or more fluorine atoms. When a fluorine atom is included in the ethylenically unsaturated urethane oligomer, it may help to form a pattern of the photosensitive resin composition.
  • the ethylenically unsaturated urethane oligomer may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the ethylenically unsaturated urethane oligomer is included in an amount of less than 1 part by weight, a problem that the residual film ratio is deteriorated due to low sensitivity may occur, and when it is included in excess of 50 parts by weight, developability is deteriorated, and a problem of lowering resolution may occur.
  • the photosensitive resin composition may further include an ethylenically unsaturated polyfunctional monomer, and specifically, may further include an ethylenically unsaturated polyfunctional monomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • an ethylenically unsaturated polyfunctional monomer is included in an amount of less than 1 part by weight, a problem that the residual film ratio is deteriorated due to low sensitivity may occur, and when it is included in excess of 50 parts by weight, developability is deteriorated and the resolution is lowered. can occur
  • the ethylenically unsaturated polyfunctional monomer is, for example, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate , pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol Triacrylate, bisphenol A diacrylate derivative, dipentaarithritol polyacrylate, and their methacrylates, fluorine-based acrylates, fluorine-based methacrylates, etc. may be used, and these may be used alone or in combination of two or more can be used, but is not limited to the above
  • the ethylenically unsaturated polyfunctional monomer may include fluorine in forming a pattern of the photosensitive resin composition.
  • the solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the acrylic copolymer, and if it is less than 10 parts by weight, other components may not be sufficiently dissolved in the solvent, and if it exceeds 500 parts by weight, the photosensitivity Since the resin composition is excessively thin, there may be a problem in that developability and adhesion are deteriorated.
  • the solvent included in the photosensitive resin composition may be a known solvent that is commonly used in the photosensitive resin composition, and specific examples thereof include propylene glycol monoethyl propionate, propylene glycol methyl ether propionate, and propylene glycol ethyl ether propionate.
  • propylene glycol alkyl ether acetates such as propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol
  • propylene glycol monoethyl propionate propylene glycol methyl ether propionate
  • propylene glycol ethyl ether propionate propylene glycol propyl ether propionate
  • a solvent of propylene glycol alkyl ether acetate such as propylene glycol butyl ether propionate can be used.
  • the photosensitive resin composition may further include a UV (Ultraviolet Rays) absorber to improve resolution.
  • the UV absorber may include, for example, benzophenones, trigins, benzotriazoles, oxanilides, and the like, but is not limited to the above examples.
  • the content of the UV absorber may be helpful in improving the resolution if used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer.
  • the photosensitive resin composition may further include a silane coupling agent to improve adhesion to the lower substrate.
  • the silane coupling agent is, for example, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane Phosphorus, 2- (3,4-epoxy cyclohexyl) ethyl trimethoxysilane, 2- (3,4-epoxy cyclohexyl) ethyl triethoxy silane, aminopropyl trimethoxysilane, aminopropyl Triethoxysilane, 3-trieth
  • the photosensitive resin composition may further include a crosslinking agent, specifically a melamine crosslinking agent, to improve heat resistance, chemical resistance, and adhesion.
  • a crosslinking agent for example, a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, or methylol urea alkyl ethers or methylol melamine alkyl ethers obtained from alcohol may be used, and specifically, the urea Monomethylol urea, dimethylol urea, etc.
  • condensation product of formaldehyde can be used as a condensation product of formaldehyde and
  • condensation product of melamine and formaldehyde hexamethylolmelamine may be used, and in addition, a partial condensation product of melamine and formaldehyde may be used.
  • methylol urea alkyl ethers a condensation product of urea and formaldehyde is obtained by reacting part or all of the methylol groups with alcohols, and specific examples thereof include monomethyl urea methyl ether and dimethyl urea methyl ether.
  • the methylol melamine alkyl ethers are those obtained by reacting a part or all of methylol groups with alcohols in a condensation product of melamine and formaldehyde, and specific examples thereof include hexamethylolmelamine hexamethyl ether, hexamethylol melamine hexabutyl Ether and the like can be used.
  • a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with a hydroxymethyl group and a methoxymethyl group a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with a butoxymethyl group and a methoxymethyl group, etc.
  • alkyl ethers can also be used, especially methylolmelamine It is preferable to use alkyl ethers.
  • Using the melanin crosslinking agent in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer may help to improve the heat resistance, chemical resistance and adhesion.
  • the photosensitive resin composition may include a surfactant to improve coatability and developability, and specifically may include at least one of a fluorine-based surfactant and a silicone surfactant.
  • the surfactant is preferably used in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the solid content excluding the solvent in the photosensitive resin composition to improve the applicability and developability.
  • the solid content of the negative photosensitive resin composition may be 10 to 50 wt %, and if it is out of the above range, there may be a problem in forming a thin film having a thickness of 2 to 4 ⁇ m.
  • a display device is a display device including a cured body of the negative photosensitive resin composition, and specifically, the cured body of the composition may be included in an optical member of the display device, for example, an interlayer insulating film.
  • the display device may include an optical member having a refractive index of 1.5 or less, and the optical member may include the curing body.
  • An example of a method of forming an insulating film using the negative photosensitive resin composition is as follows. First, the low refractive index negative photosensitive resin composition of the present invention is applied to the surface of a substrate by a spray method, a slit coater method, a roll coater method, a rotation coating method, etc., and the solvent is removed by prebaking to form a coating film. At this time, the heat treatment is preferably performed at a temperature of 80 to 100 °C 1 to 5 minutes. Then, a predetermined pattern is formed by irradiating visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc.
  • an aqueous alkali solution as the developer, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate; primary amines such as n-propylamine; secondary amines such as diethylamine and n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; Alternatively, an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate
  • primary amines such as n-propylamine
  • secondary amines such as diethylamine and n-propylamine
  • the developer is used by dissolving an alkaline compound at a concentration of 0.01 to 10 wt%, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added.
  • a water-soluble organic solvent such as methanol or ethanol and a surfactant
  • washing with ultrapure water for 50 to 180 seconds to remove unnecessary parts and drying to form a pattern selectively irradiating light such as ultraviolet rays to the formed pattern, and heating the pattern in an oven, etc.
  • a final interlayer insulating film can be obtained by curing the device at a temperature of 80 to 150° C. for 30 to 180 minutes.
  • the acrylic copolymer was cooled to room temperature (23° C.), and 200 parts by weight of propylene glycol monomethyl ether acetate was added thereto, followed by distillation under reduced pressure.
  • the tetrahydrofuran content is 0.5 wt % or less through GC (Gas Chromatography) analysis, vacuum distillation is terminated. Further, propylene glycol monomethyl ether acetate is added so that the solid content concentration is 30% by weight.
  • a polymer solution having a weight average molecular weight of the polymer of 5,000 was prepared. In this case, the weight average molecular weight is a polystyrene reduced average molecular weight measured using GPC (Gel Permeation Chromatography).
  • n is an integer of 0 to 9
  • n is an integer of 1 to 10
  • n is an integer of 0 to 9
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • n is an integer of 1 to 10
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 30 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • R is an organic compound having an alkyl, alkene, or allyl structure as an integer of 0 to 10 C
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
  • Example 1 Based on 10 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 30 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 40 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • Example 1 Based on 50 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
  • a negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
  • Example 4 In the same negative photosensitive resin composition as in Example 4, a coating solution was prepared except for the fluorine-based ethylenically unsaturated urethane oligomer.
  • a coating solution was prepared except for the ion initiator in the same negative photosensitive resin composition as in Example 4.
  • a coating solution was prepared except for the UV absorber in the same negative photosensitive resin composition as in Example 4.
  • Example 1 An acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 1 in Formula 2 is applied, and the remainder is Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2 above, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • Example 1 An acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 5 in Formula 2 is applied, and the remainder is Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2 above, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2 above, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • Example 1 An acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 1 in Formula 3 is applied, and the remainder is Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • Example 1 An acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 5 in Formula 3 is applied, and the remainder is Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • an acrylic copolymer obtained by copolymerization of 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 9 in Formula 3, and the remainder was Example 1
  • the same negative photosensitive resin composition coating solution was prepared.
  • Adhesion After applying the negative photosensitive resin composition solution prepared in Examples 1 to 80 and Comparative Examples 1 to 110 using a spin coater on the SiNx substrate, pre-baked on a hot plate at 85° C. for 120 seconds to 2.0 A mu m film was formed. The coated film was exposed with an exposure dose corresponding to the sensitivity (Eop) of each sample at 200 mW/cm 2 intensity condition with Canon exposure machine MPA-600. Then, for final curing, it was heated at 85° C. for 120 minutes in an oven to obtain a substrate for measuring adhesion. Adhesion was evaluated by cross cut Adhesion test (ASTM D3359).
  • Examples 1 to 177 of the present invention exhibit superiority in refractive index, resolution, and adhesive force compared to Comparative Examples 1 to 13, and in particular, Examples 1 to 80 in Examples 81 to Compared to 177, it shows better refractive index, resolution, and adhesion.

Abstract

The present invention relates to a negative photo-sensitive resin composition with low-temperature curability and a low refractive index and, more specifically, to a negative photo-sensitive resin composition comprising: an acrylic copolymer comprising a repeating unit derived from a first unsaturated compound containing a heat-curable functional group and a repeating unit derived from a second unsaturated compound containing fluorine, along with a photo-initiator and a solvent, so that the resin composition is curable at 150℃ or lower and has a refractive index of 1.50 or less.

Description

저온 경화가 가능하며 굴절률이 낮은 네가티브 감광성 수지 조성물Negative photosensitive resin composition capable of low-temperature curing and low refractive index
본 출원은 2020년 12월 31일자로 출원된 한국특허출원 제10-2020-0189889호에 대한 우선권주장출원으로서, 해당 출원의 명세서 및 도면에 개시된 모든 내용은 인용에 의해 본 출원에 원용된다.This application is an application for priority claiming Korean Patent Application No. 10-2020-0189889 filed on December 31, 2020, and all contents disclosed in the specification and drawings of the application are incorporated herein by reference.
본 발명은 150℃ 이하의 저온에서 경화가 가능하고 굴절률이 낮은 특성을 가진 네가티브 감광성 수지 조성물 및 이의 경화물을 포함하는 표시장치에 관한 것이다.The present invention relates to a negative photosensitive resin composition capable of being cured at a low temperature of 150° C. or less and having a low refractive index, and a display device including a cured product thereof.
구조화된 프리즘을 갖는 투과성 광학 필름의 경우, 프리즘 구조를 이루고 있는 수지의 굴절률에 의하여 휘도 상승율이 변한다. 종래의 일반적으로 프리즘을 구성하는 수지의 경우 상층부, 하층부에 위치한 물질의 굴절률 차이에 의해서 광손실이 발생한다.In the case of a transmissive optical film having a structured prism, the luminance increase rate is changed according to the refractive index of the resin constituting the prism structure. In the case of a conventional resin constituting a prism, light loss occurs due to a difference in refractive index of materials located in the upper and lower layers.
기존의 감광성 수지 조성물의 경우 단막 형태의 필름으로 저굴절 특성을 확보하였으나 패턴 특성이 불가한 문제점을 가지고 있다. In the case of the conventional photosensitive resin composition, a single film type film secured low refractive index, but it has a problem in that pattern characteristics are impossible.
그리고 기존 LCD 및 OLED에서 사용하고 있던 유리기판을 플라스틱 필름으로 대체하여, 접고 펼 수 있는 유연성을 부여된 플렉서블 디스플레이에서 컬러필터의 평탄화 및 층간 절연막으로 사용되는 감광성 수지는 저온에서 공정이 진행되므로, 저온에서 경화가 가능한 감광성 수지 조성물이 필요한 실정이다.In addition, the photosensitive resin used as an interlayer insulating film and flattening of a color filter in a flexible display that has been given flexibility to fold and unfold by replacing the glass substrate used in the existing LCD and OLED with a plastic film is processed at low temperature. There is a need for a photosensitive resin composition that can be cured in
본 발명의 목적은 150℃ 이하의 저온에서 경화가 가능하고, 굴절률이 1.50 이하의 유기화합물만으로 이루어진 저굴절 감광성 수지 조성물을 제공하는 것이다.It is an object of the present invention to provide a low-refractive photosensitive resin composition that can be cured at a low temperature of 150° C. or less and has a refractive index of only 1.50 or less of an organic compound.
본 발명의 또 다른 목적은 상기 감광성 수지 조성물의 경화체를 포함하는 표시장치를 제공하는 것이다.Another object of the present invention is to provide a display device including a cured product of the photosensitive resin composition.
상기 과제를 해결하기 위하여 본 발명의 일 실시예에 따른 네가티브 감광성 수지 조성물은 열경화성 작용기를 포함하는 제1 불포화 화합물로부터 유래된 반복단위와 불소를 포함하는 제2 불포화 화합물로부터 유래된 반복단위를 포함하는 아크릴계 공중합체, 광개시제 및 용매를 포함한다.In order to solve the above problems, the negative photosensitive resin composition according to an embodiment of the present invention includes a repeating unit derived from a first unsaturated compound containing a thermosetting functional group and a repeating unit derived from a second unsaturated compound containing fluorine. an acrylic copolymer, a photoinitiator and a solvent.
상기 아크릴계 공중합체는 상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위를 각각 5 내지 30 중량%로 포함할 수 있다.The acrylic copolymer may include 5 to 30% by weight of each of the repeating units derived from the first and second unsaturated compounds.
상기 아크릴계 공중합체는 상기 제1 불포화 화합물로부터 유래된 반복단위를 10 내지 30 중량%, 제2 불포화 화합물로부터 유래된 반복단위를 5 내지 30 중량% 로 포함할 수 있다.The acrylic copolymer may include 10 to 30% by weight of the repeating unit derived from the first unsaturated compound and 5 to 30% by weight of the repeating unit derived from the second unsaturated compound.
상기 아크릴계 공중합체는 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위를 더 포함할 수 있으며, 구체적으로 1 내지 50 중량%로 포함할 수 있다.The acrylic copolymer may further include a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, and specifically may be included in an amount of 1 to 50% by weight.
상기 아크릴계 공중합체는 상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위를 각각 5 내지 30 중량%, 올레핀 불포화 화합물로부터 유래된 반복단위를 1 내지 50 중량%로 포함할 수 있다.The acrylic copolymer may include 5 to 30 wt% of the repeating unit derived from the first and second unsaturated compounds, respectively, and 1 to 50 wt% of the repeating unit derived from the olefinically unsaturated compound.
상기 제1 불포화 화합물은 에폭시기를 갖는 직쇄 또는 측쇄 지방족 구조 또는 에폭시기를 갖는 지환족 구조를 포함할 수 있다.The first unsaturated compound may include a linear or branched aliphatic structure having an epoxy group or an alicyclic structure having an epoxy group.
상기 제1 불포화 화합물은 하기 화학식 1 내지 화학식 3으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함할 수 있다.The first unsaturated compound may include one or more structures selected from the group consisting of Chemical Formulas 1 to 3 below.
[화학식 1][Formula 1]
Figure PCTKR2021018681-appb-img-000001
Figure PCTKR2021018681-appb-img-000001
[화학식 2][Formula 2]
Figure PCTKR2021018681-appb-img-000002
Figure PCTKR2021018681-appb-img-000002
[화학식 3][Formula 3]
Figure PCTKR2021018681-appb-img-000003
Figure PCTKR2021018681-appb-img-000003
이때 상기 화학식 2에서 n은 1 내지 10의 정수이고, 상기 화학식 3에서 R은 탄소수 0 내지 10의 알킬, 알켄, 알릴 구조 중 하나 이상을 가지는 유기기이다.In this case, in Formula 2, n is an integer of 1 to 10, and R in Formula 3 is an organic group having at least one of an alkyl, alkene, and allyl structure having 0 to 10 carbon atoms.
상기 제2 불포화 화합물은 하기 화학식 4 내지 화학식 6으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함하는 것일 수 있다.The second unsaturated compound may include one or more structures selected from the group consisting of Chemical Formulas 4 to 6 below.
[화학식 4][Formula 4]
Figure PCTKR2021018681-appb-img-000004
Figure PCTKR2021018681-appb-img-000004
[화학식 5][Formula 5]
Figure PCTKR2021018681-appb-img-000005
Figure PCTKR2021018681-appb-img-000005
[화학식 6][Formula 6]
Figure PCTKR2021018681-appb-img-000006
Figure PCTKR2021018681-appb-img-000006
이때 상기 화학식 4에서 n은 0 내지 9의 정수이고, 상기 화학식 5에서 n은 1 내지 10의 정수이며, 상기 화학식 6에서 n은 0 내지 9의 정수이다.In this case, in Formula 4, n is an integer of 0 to 9, in Formula 5, n is an integer of 1 to 10, and in Formula 6, n is an integer of 0 to 9.
상기 아크릴계 공중합체의 중량평균분자량(Mw)은 1,000 내지 10,000일 수 있다.The weight average molecular weight (Mw) of the acrylic copolymer may be 1,000 to 10,000.
상기 광개시제는 상기 아크릴계 공중합체 100 중량부에 대하여, 0.1 내지 30 중량부로 감광성 수지 조성물에 포함될 수 있다.The photoinitiator may be included in the photosensitive resin composition in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.
상기 네가티브 감광성 수지 조성물은 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 에틸렌성 불포화 우레탄 올리고머를 더 포함할 수 있다.The negative photosensitive resin composition may further include an ethylenically unsaturated urethane oligomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
상기 에틸렌성 불포화 우레탄 올리고머는 하나 이상의 불소 원자를 포함할 수 있다.The ethylenically unsaturated urethane oligomer may contain one or more fluorine atoms.
상기 네가티브 감광성 수지 조성물은 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 에틸렌성 불포화 다관능 모노머를 더 포함할 수 있다.The negative photosensitive resin composition may further include an ethylenically unsaturated polyfunctional monomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
상기 에틸렌성 불포화 다관능 모노머는 불소를 포함할 수 있다.The ethylenically unsaturated polyfunctional monomer may include fluorine.
상기 용매는 상기 아크릴계 공중합체 100 중량부에 대하여, 10 내지 500 중량부로 포함될 수 있으며, 예를 들어, 상기 용매는 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디프로필렌글리콜디메틸에테르, 디포로필렌글리콜디에틸에테르, 부틸렌글리콜모노메틸에테르, 부틸렌글리콜모노에틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에틸에테르, 트리에틸렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르로 이루어지는 군으로부터 선택되는 1종 이상일 수 있다.The solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the acrylic copolymer, for example, the solvent is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol. Ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diphoropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, diethylene Glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methyl It may be at least one selected from the group consisting of hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether and dipropylene glycol methylhexyl ether.
본 발명의 다른 일 실시예에 따른 표시장치는 상기 네가티브 감광성 수지 조성물의 경화체를 포함한다. 구체적으로 상기 표시장치는 1.5 이하의 굴절률을 가진 광학부재를 포함하며,상기 광학부재는 상기 경화체를 포함할 수 있다.A display device according to another embodiment of the present invention includes a cured product of the negative photosensitive resin composition. Specifically, the display device may include an optical member having a refractive index of 1.5 or less, and the optical member may include the curing body.
본 발명의 감광성 수지 조성물은 150℃ 이하에서 경화가 가능하여 저온에서도 포토레지스 공정에 의한 패턴 형성이 가능하며, 1.50 이하의 굴절률이 가능하여 디스플레이 소재로서 층간 굴절률에 의한 광손실을 줄이고 패널의 휘도 상승을 억제하여 배터리 수명을 늘일 수 있는 효과가 있다.The photosensitive resin composition of the present invention can be cured at 150° C. or less, so it is possible to form a pattern by a photoresist process even at low temperatures, and a refractive index of 1.50 or less is possible, so as a display material, light loss due to interlayer refractive index is reduced and panel brightness is increased This has the effect of increasing battery life by suppressing it.
이하, 도면을 참고하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to the drawings.
이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.
따라서, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고, 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들은 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Accordingly, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiment of the present invention, and do not represent all the technical spirit of the present invention, so at the time of the present application, they can be replaced It should be understood that various equivalents and modifications may exist.
본 발명의 일 실시예에 따른 네가티브 감광성 수지 조성물은 150℃ 이하에서 경화가 가능하면서도 저굴절 특성을 갖기 위하여 열경화성 작용기를 포함하는 제1 불포화 화합물로부터 유래된 반복단위, 불소를 포함하는 제2 불포화 화합물로부터 유래된 반복단위를 포함하는 아크릴계 공중합체, 광개시제 및 상기 조성물을 용해 시킬수 있는 용매를 포함한다. The negative photosensitive resin composition according to an embodiment of the present invention is a repeating unit derived from a first unsaturated compound containing a thermosetting functional group in order to have low refractive properties while being curable at 150° C. or less, and a second unsaturated compound containing fluorine It contains an acrylic copolymer including a repeating unit derived from, a photoinitiator, and a solvent capable of dissolving the composition.
상기 아크릴계 공중합체는 상기 감광성 수지 조성물이 현상되는 과정에서 스컴이 발생하지 않으면서 패턴이 용이하게 형성되도록 하는 역할을 한다.The acrylic copolymer serves to facilitate the formation of a pattern without scum occurring in the process of developing the photosensitive resin composition.
상기 아크릴계 공중합체는 상기 제1 불포화 화합물로부터 유래된 반복단위를 5 내지 30 중량%, 구체적으로는 10 내지 30 중량%로 포함하는 것일 수 있다. 상기 제1 불포화 화합물로부터 유래된 반복단위가 5중량% 미만으로 포함되면 조성물의 열가교성이 떨어지게 되어 상기 조성물이 경화된 필름의 접착력이 취약해지는 문제가 발생할 수 있으며, 30 중량%를 초과하는 경우 상기 조성물이 경화된 필름을 사용한 디스플레이 제품의 해상도가 떨어지고, 조성물의 안정성이 떨어지는 문제가 발생할 수 있다.The acrylic copolymer may include 5 to 30% by weight of the repeating unit derived from the first unsaturated compound, specifically 10 to 30% by weight. When the amount of the repeating unit derived from the first unsaturated compound is less than 5% by weight, the thermal crosslinking property of the composition is deteriorated, so that the adhesive strength of the cured film of the composition may be weakened, and when it exceeds 30% by weight, the above The resolution of a display product using a film in which the composition is cured is lowered, and there may be problems in which the stability of the composition is lowered.
상기 아크릴계 공중합체는 상기 제2 불포화 화합물로부터 유래된 반복단위를 5 내지 30 중량%로 포함하는 것일 수 있다. 상기 제2 불포화 화합물로부터 유래된 반복단위가 5 중량% 미만으로 포함되면 상기 조성물의 굴절률이 1.50보다 높아지는 문제가 발생할 수 있으며, 30 중량%를 초과하는 경우 상기 조성물을 현상하는 과정에서 백탁이 발생할 수 있을뿐만 아니라, 공중합 반응 중 겔화(gelation)가 되는 문제가 발생할 수 있다.The acrylic copolymer may include 5 to 30% by weight of the repeating unit derived from the second unsaturated compound. If the amount of the repeating unit derived from the second unsaturated compound is less than 5% by weight, a problem may occur that the refractive index of the composition becomes higher than 1.50, and if it exceeds 30% by weight, cloudiness may occur in the process of developing the composition. In addition, there may be a problem of gelation during the copolymerization reaction.
상기 아크릴계 공중합체는 상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위뿐만 아니라 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위를 더 포함하는 것일 수 있다. 상기 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위는 아크릴계 공중합체에 포함되어 상기 감광성 수지 조성물의 알칼리 수용액에 대한 용해도를 향상시키는 효과를 부여한다.The acrylic copolymer may further include repeating units derived from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or mixtures thereof as well as repeating units derived from the first and second unsaturated compounds. The repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is included in the acrylic copolymer to provide an effect of improving the solubility of the photosensitive resin composition in an aqueous alkali solution.
상기 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위는 1 내지 50 중량%, 보다 구체적으로는 5 내지 40 중량%로 상기 아크릴 공중합체에 포함될 수 있다. 상기 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위가 상기 아크릴 공중합체에 1 중량% 미만으로 포함되는 경우, 상기 감광성 수지 조성물의 현상액인 알칼리 수용액에 용해하기 어려운 문제가 발생할 수 있으며, 50 중량% 초과로 포함되는 경우에는 상기 감광성 수지 조성물의 현상액인 알칼리 수용액에 대한 용해성이 지나치게 커지는 문제가 발생할 수 있다.The repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof may be included in the acrylic copolymer in an amount of 1 to 50 wt%, more specifically 5 to 40 wt%. When the repeating unit derived from the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is included in the acrylic copolymer in an amount of less than 1% by weight, it may be difficult to dissolve in an aqueous alkali solution as a developer of the photosensitive resin composition. And, when it is included in more than 50% by weight, the solubility of the photosensitive resin composition in an aqueous alkali solution, which is a developer, may be excessively increased.
상기 불포화 카르본산 또는 불포화 카르본산 무수물는 예를 들어 아크릴산, 메타크릴산, 말레인산, 푸마르산, 시트라콘산, 메타콘산, 이타콘산 및 이들의 불포화 디카르본산의 무수물 중 하나 일 수 있으며, 상기 불포화 카르본산 또는 불포화 카르본산 무수물을 단독으로 사용할 수도 있고, 2종 이상을 혼합하여 사용할 수도있다. 예를 들어 아트릴산, 메타크릴산, 또는 무수말레인산을 사용하는 것이 공중합 반응성과 현상액인 알칼리 수용액에 대한 용해성에 있어 좋다.The unsaturated carboxylic acid or unsaturated carboxylic acid anhydride may be, for example, one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and anhydrides of these unsaturated dicarboxylic acids, and the unsaturated carboxylic acid Or an unsaturated carboxylic acid anhydride may be used individually, and 2 or more types may be mixed and used for it. For example, using acrylic acid, methacrylic acid, or maleic anhydride is good in terms of copolymerization reactivity and solubility in aqueous alkali solution as a developer.
상기 아크릴계 공중합체는 올레핀계 불포화 화합물로부터 유래된 반복단위를 더 포함하는 것일 수 있다. 상기 올레핀계 불포화 화합물은 상기 아크릴계 공중합체에 포함되어 상기 아크릴 공중합체의 경화물의 투명도를 향상시켜 추후 디스플레이 장치의 해상도를 더욱 높이는 역할을 한다.The acrylic copolymer may further include a repeating unit derived from an olefinically unsaturated compound. The olefin-based unsaturated compound is included in the acrylic copolymer to improve transparency of the cured product of the acrylic copolymer, thereby further increasing the resolution of a display device in the future.
상기 올레핀 불포화 화합물로부터 유래된 반복단위는 1 내지 50 중량%로 상기 아크릴 공중합체에 포함될 수 있다. 상기 올레핀계 불포화 화합물로부터 유래된 반복단위가 상기 아크릴 공중합체에 1 중량% 미만으로 포함되는 경우, 상기 감광성 수지 조성물이 경화된 필름이 디스플레이 장치에 사용될 때 상기 디스플레이장치의 해상도가 떨어지는 문제가 발생할 수 있으며, 상기 필름의 내열성이 떨어지는 문제 또한 발생할 수 있다. 또한 상기 올레핀계 불포화 화합물로부터 유래된 반복단위가 상기 아크릴 공중합체에 50 중량% 초과로 포함되는 경우 상기 아크릴계 공중합체가 현상액인 알칼리 수용액에 용해되기 어려운 문제가 발생할 수 있다.The repeating unit derived from the olefin unsaturated compound may be included in the acrylic copolymer in an amount of 1 to 50 wt%. When the repeating unit derived from the olefinically unsaturated compound is included in the acrylic copolymer in an amount of less than 1% by weight, when the film in which the photosensitive resin composition is cured is used in a display device, a problem of lowering the resolution of the display device may occur. In addition, a problem of poor heat resistance of the film may also occur. In addition, when the repeating unit derived from the olefinically unsaturated compound is included in the acrylic copolymer in an amount of more than 50% by weight, it may be difficult to dissolve the acrylic copolymer in an aqueous alkali solution as a developer.
상기 올레핀계 불포화 화합물은 구체적인 예로 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 사이클로헥실 메타크릴레이트, 2-메틸사이클로 헥실메타크릴레이트, 디사이클로펜테닐아크릴레이트, 디사이클로펜타닐아크릴레이트, 디사이클로펜테닐메타크릴레이트, 디사이클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 디사이클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이트, 사이클로헥실아크릴레이트, 2-메틸사이클로헥실아크릴레이트, 디사이클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트, 스티렌, σ-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐톨루엔, p-메톡시 스티렌, 1,3-부타디엔, 이소프렌, 및 2,3-디메틸 1,3-부타디엔, 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, 및 p-비닐벤질글리시딜에테르 및 메타크릴산 3,4-에폭시 사이클로헥실 중 하나 이상을 사용할 수 있으나, 상기 예로 한정되는 것은 아니다.Specific examples of the olefinically unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl Methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1 -Adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboronyl Acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene , 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate , α-n-butylacrylic acid glycidyl, acrylic acid-β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl , acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7- At least one of epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether and 3,4-epoxy cyclohexyl methacrylic acid may be used, but the above Examples are not limited.
상기 제1 불포화 화합물은 열경화성 작용기로서 구체적으로 에폭시기를 포함할 수 있다. 보다 구체적으로 예를 들어 옥세탄(oxane), 테트라하이드로퓨란(THF) 등이 포함될 수 있으나, 이에 한정되는 것은 아니다.The first unsaturated compound may specifically include an epoxy group as a thermosetting functional group. More specifically, for example, oxane, tetrahydrofuran (THF), etc. may be included, but is not limited thereto.
상기 제1 불포화 화합물은 구체적으로 에폭시기를 갖는 직쇄 또는 측쇄 지방족 구조 또는 에폭시기를 갖는 지환족 구조를 포함하는 것이 좋으며, 방향족 고리를 포함하지 않는 것이 좋다. 방향족 고리를 갖을 경우 굴절률이 증가하는 문제가 발생할 수 있다.Specifically, the first unsaturated compound preferably includes a linear or branched aliphatic structure having an epoxy group or an alicyclic structure having an epoxy group, and preferably does not include an aromatic ring. In the case of having an aromatic ring, a problem of increasing the refractive index may occur.
상기 제1 불포화 화합물은 구체적으로 에폭시기를 1개 포함할 수 있으며, 에폭시기가 2개 이상인 경우 상기 아크릴계 공중합체가 겔화되는 문제가 발생할 수 있다.The first unsaturated compound may specifically include one epoxy group, and when there are two or more epoxy groups, a problem in that the acrylic copolymer is gelled may occur.
상기 제1 불포화 화합물은 보다 구체적으로 하기 화학식 1 내지 화학식 3으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함하는 것일 수 있으나, 하기 화학식 1 내지 3 구조에 제한되는 것은 아니며, 하기 화학식 1 내지 3 구조에서 지환족 탄화수소 부분이 지방족으로 대체될 수 있다. 하지만 하기 화학식 1 내지 3 구조에서 지환족 탄화수소 부분이 방향족 탄화수소로 치환된 구조의 경우 조성물의 저굴절 특성이 나오지 않는 문제가 발생할 수 있다.The first unsaturated compound may include one or more structures selected from the group consisting of more specifically the following Chemical Formulas 1 to 3, but is not limited to the following Chemical Formulas 1 to 3 structures, and the following Chemical Formulas 1 to 3 structures In the alicyclic hydrocarbon moiety may be replaced by an aliphatic. However, in the case of a structure in which an alicyclic hydrocarbon portion is substituted with an aromatic hydrocarbon in the structures of Chemical Formulas 1 to 3, there may be a problem in that the composition does not exhibit low refractive properties.
[화학식 1][Formula 1]
Figure PCTKR2021018681-appb-img-000007
Figure PCTKR2021018681-appb-img-000007
[화학식 2][Formula 2]
Figure PCTKR2021018681-appb-img-000008
Figure PCTKR2021018681-appb-img-000008
[화학식 3][Formula 3]
Figure PCTKR2021018681-appb-img-000009
Figure PCTKR2021018681-appb-img-000009
상기 화학식 2에서 n은 1 내지 10의 정수, 바람직하게 1 내지 5의 정수이고, 상기 화학식 3에서 R은 탄소수 0 내지 10의 알킬, 알켄, 알릴 구조 중 하나 이상을 가지는 유기기이다. 상기 화학식 2의 n이 1 내지 5인 경우 상기 감광성 수지 조성물이 경화된 필름의 해상도가 유리한 장점이 있으나, 상기 n에 제한되는 것은 아니다.In Formula 2, n is an integer of 1 to 10, preferably an integer of 1 to 5, and R in Formula 3 is an organic group having at least one of an alkyl, alkene, and allyl structure having 0 to 10 carbon atoms. When n in Formula 2 is 1 to 5, the resolution of the film in which the photosensitive resin composition is cured is advantageous, but is not limited to n.
상기 제2 불포화 화합물은 불소와 함께 1 내지 2개의 아크릴레이트기를 포함하는 구조를 가진 것일 수 있다. 상기 불소는 아크릴 공중합체에 포함되어 감광성 수지 조성물의 굴절률을 크게 낮추는 역할을 한다. 아크릴레이트기가 3개 이상으로 포함되는 경우 제2 불포화 화합물에 제1 불포화 화합물이 과도하게 중합반응 할 수 있어 제2 불포화 화합물의 불소가 상기 굴절률을 낮추는 역할을 할 수는 있으나 패턴(해상도) 특성이 취약해지는 문제가 발생할 수 있다.The second unsaturated compound may have a structure including 1 to 2 acrylate groups together with fluorine. The fluorine is included in the acrylic copolymer to significantly lower the refractive index of the photosensitive resin composition. When three or more acrylate groups are included, the first unsaturated compound may be excessively polymerized with the second unsaturated compound, so that fluorine in the second unsaturated compound may serve to lower the refractive index, but the pattern (resolution) characteristics may be poor. Vulnerability can be a problem.
상기 제2 불포화 화합물은 구체적인 예를 들어 하기 화학식 4 내지 화학식 6으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함하는 것일 수 있다. 하지만 하기 구조에 제한되는 것은 아니다.The second unsaturated compound may include, for example, one or more structures selected from the group consisting of Chemical Formulas 4 to 6 below. However, it is not limited to the following structure.
[화학식 4][Formula 4]
Figure PCTKR2021018681-appb-img-000010
Figure PCTKR2021018681-appb-img-000010
[화학식 5][Formula 5]
Figure PCTKR2021018681-appb-img-000011
Figure PCTKR2021018681-appb-img-000011
[화학식 6][Formula 6]
Figure PCTKR2021018681-appb-img-000012
Figure PCTKR2021018681-appb-img-000012
상기 화학식 4에서 n은 0 내지 9의 정수이고, 상기 화학식 5에서 n은 1 내지 10의 정수이며, 상기 화학식 6에서 n은 0 내지 9의 정수이다.In Formula 4, n is an integer of 0 to 9, In Formula 5, n is an integer of 1 to 10, and in Formula 6, n is an integer of 0 to 9.
상기 제2 불포화 화합물은 불소 원자를 23개 이하로 포함하는 것이 상기 감광성 수지 조성물의 패턴 형성과 상기 감광성 수지 조성물의 굴절률을 1.5 이하로 하는데 도움을 줄 수 있다.When the second unsaturated compound contains 23 or less fluorine atoms, it may help to form a pattern of the photosensitive resin composition and set the refractive index of the photosensitive resin composition to 1.5 or less.
상기 아크릴계 공중합체는 중량평균분자량(Mw), 구체적으로 폴리스티렌 환산중량평균분자량(Mw)이 1,000 내지 10,000일 수 있다. 상기 중량평균분자량(Mw)이 1,000 미만인 경우 상기 감광성 수지 조성물의 현상성 및 잔막율이 저하되는 문제가 발생할 수 있으며, 패턴 현상과 내열성이 떨어지는 문제가 있다. 상기 중량평균분자량(Mw)이 10,000을 초과하는 경우에는 패턴 현상성이 떨어지는 문제가 발생할 수 있다.The acrylic copolymer may have a weight average molecular weight (Mw), specifically, a polystyrene equivalent weight average molecular weight (Mw) of 1,000 to 10,000. When the weight average molecular weight (Mw) is less than 1,000, the developability and the remaining film rate of the photosensitive resin composition may be deteriorated, and pattern development and heat resistance may be deteriorated. When the weight average molecular weight (Mw) exceeds 10,000, a problem of poor pattern developability may occur.
상기 광개시제는 상기 아크릴계 공중합체 100 중량부에 대하여, 0.1 내지 30 중량부로 포함하는 것이 좋다. 상기 광개시제가 0.1 중량부 미만으로 포함되는 경우 낮은 감도로 인해 잔막율이 나빠지는 문제가 발생할 수 있으며, 30 중량부를 초과하는 경우 현상성이 떨어지고, 상기 감광성 수지 조성물의 경화물의 해상도가 저하되는 문제가 발생할 수 있다. The photoinitiator is preferably included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer. When the photoinitiator is included in an amount of less than 0.1 parts by weight, there may be a problem that the residual film ratio is deteriorated due to low sensitivity, and when it exceeds 30 parts by weight, developability is deteriorated, and the resolution of the cured product of the photosensitive resin composition is lowered. can occur
상기 광개시제는 구체적으로 라디칼 광개시제를 포함할 수 있으며, 예를 들어, 4-페녹시디클로로아세토페논, 4-t-부틸-디클로로아세토페논, 디에톡시아세토페논, p-디메틸아니노아세토페논, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 1-하이드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1-온, 2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부타논 등의 아세토페논계 화합물, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤질디메틸케탈 등의 벤조인계 화합물, 벤조페논, 벤조일안식향산, 벤조일안식향산메틸, 4-페닐벤조페논, 하이드록시벤조페논, 아크릴화 벤조페논, 4-벤조일-4'-메틸디페닐설파이드, 3,3',4,4'-테트라(t-부틸포옥시카르보닐)벤조페논 등의 벤조페논계 화합물, 티옥산톤, 2-클로로티옥산톤, 2-메틸디옥산톤, 이소프로필티옥산톤, 2,4-디이소프로필티옥산톤, 2,4-디에틸티옥산톤 등의 티옥산톤계 화합물, 2,4,6-트리클로로-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-피페노닐-4,6-비스(트리클로로메틸)-s-트리아진, 2,4-비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)- 4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시-나프토-1-일)- 4,6-비스(트리클로로메틸)-s-트리아진, 2,4-트리클로로메틸-(피페로닐)-6-트리아진, 2,4-트리클로로메틸(4'-메톡시스티릴)-6-트리아진 등의 트리아진계 화학물, 2-(O-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온, 1-(O-아케틸옥심) -1-[9-에틸-6-(2-메틸벤조일)-9H-카바졸-3-일]-에탄온, O-에톡시카르보닐-α-옥시아미노-1-페닐프로판-1-온, 1,2-옥탄디온, 2-디메틸아미노-2-(4-메틸벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온, 1-(4-페닐술파닐페닐)-부탄-1,2-디온-2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1,2-디온-2-옥심-O-벤조에이트, 1-(4-페닐술파닐페닐)-옥탄-1-온옥심-O-아세테이트, 1-(4-페닐술파닐페닐)-부탄-1-온옥심-O-아세테이트, 2-(O-벤조일옥심)-1-[4-(페닐티오)p-메틸페닐]-1,2-옥탄디온, 2-(O-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-페닐디온, 2-(O-아세틸옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온, 2-(O-아세틸옥심)-1-[4-(페닐티오)페닐]-1,2-페닐디온, 2-(O-아세틸옥심)-1-[4-(페닐티오)페닐]-1,2-메틸디온, O-(아세틸)-N-(1-페닐-2-옥소-2-(4'-메톡시-나프틸)에틸리덴)하이드록실아민, 등의 옥심에스테르계 화합물, 비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드 등의 포스핀계 화합물, 2,2'-비스(o-클로로페닐)-4,5,4',5'-테트라페닐-1,2'-비이미다졸, 2,2'-비스(o-메톡시페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(o-메톡시페닐)-4,4',5,5'-테트라(p-메틸페닐)비이미다졸 등의 이미다졸계 화합물, 9,10-페난트렌퀴논, 캠퍼퀴논, 에틸안트라퀴논 등의 퀴논계 화합물, 보레이트계 화합물, 카바졸계 화합물 및 티타노센계 화합물을 사용 할 수 있으며, 이들을 단독 또는 2종 이상을 혼합하여 사용할 수 있으나, 상기 예시에 한정되지 않는다.The photoinitiator may specifically include a radical photoinitiator, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaninoacetophenone, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morph Polynopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl Acetophenone compounds such as ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal Benzoin compounds such as benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4, Benzophenone compounds such as 4'-tetra(t-butylpooxycarbonyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methyldioxanthone, isopropylthioxanthone, 2,4- Thioxanthone-based compounds such as diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-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-pipenonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2 -(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)- 4,6-bis(trichloro methyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine, etc. Triazine-based chemicals, 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-phenylpropane-1- One, 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenyl) Sulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate; 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate, 2-(O-benzoyl Oxime)-1-[4-(phenylthio)p-methylphenyl]-1,2-octanedione, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-phenyl Dione, 2-(O-acetyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-acetyloxime)-1-[4-(phenylthio)phenyl] -1,2-phenyldione, 2-(O-acetyloxime)-1-[4-(phenylthio)phenyl]-1,2-methyldione, O-(acetyl)-N-(1-phenyl-2 -oxime ester compounds such as oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6 -Phosphine compounds such as trimethylbenzoyl-diphenyl-phosphine oxide, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4', Imidazole compounds such as 5,5'-tetra(p-methylphenyl)biimidazole, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds and titano Sen-based compounds may be used, and these may be used alone or in combination of two or more, but the present invention is not limited thereto.
상기 광개시제는 상기 감광성 조성물이 저온공정에서 내화학성과 접착력이 향상되도록 하기 위하여 상기 라디칼 광개시제와 함께 이온광개시제를 각각 1종 이상씩 포함할 수 있다. 구체적으로 상기 이온광개시제는 양이온 광개시제, 음이온 광개시제 또는 이들의 혼합물일 수 있으며, 예를 들어 페닐(4-메톡시페닐)요오드늄육불화인, N,N-디메틸-N-벤질트리플루오로메탄술폰산, 4-메틸페닐(4-(2-메틸프로필페닐))요오드늄육불화인, 및 페닐(4-메톡시페닐)요오드늄육불화비소를 사용할 수 있으며 이들은 필요에 따라 1종 이상 혼합 사용이 가능하나, 상기 예시에 한정되지 않는다. 상기 내화학성 및 접착력 향상을 위하여 상기 이온 광개시제는 상기 아크릴계 공중합체 100 중량부에 대하여 0.5 내지 10 중량부로 사용하는 것이 좋다.The photoinitiator may include at least one ion photoinitiator together with the radical photoinitiator in order to improve chemical resistance and adhesion of the photosensitive composition in a low temperature process. Specifically, the ion photoinitiator may be a cationic photoinitiator, an anionic photoinitiator, or a mixture thereof, for example, phenyl (4-methoxyphenyl) iodonium hexafluoride, N,N-dimethyl-N-benzyltrifluoromethanesulfonic acid, 4-methylphenyl (4- (2-methylpropylphenyl)) iodonium hexafluoride, and phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride can be used, and one or more of these can be mixed and used as needed. It is not limited to an example. In order to improve the chemical resistance and adhesion, the ionic photoinitiator is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.
상기 감광성 수지 조성물은 저굴절 특성을 확보하기 위하여 에틸렌성 불포화 우레탄 올리고머를 더 포함할 수 있다. The photosensitive resin composition may further include an ethylenically unsaturated urethane oligomer to secure low refractive properties.
상기 에틸렌성 불포화 우레탄 올리고머는 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부, 특히 5 내지 30 중량부로 포함하는 것이 좋다. 상기 에틸렌성 불포화 우레탄 올리고머의 함량이 1 중량부 미만인 경우 상기 감광성 수지 조성물의 저굴절 특성 확보가 어렵고 잔막율이 나빠지는 문제가 발생할 수 있으며, 50 중량부를 초과하는 경우 현상성이 떨어지고, 해상도가 저하되는 문제가 발생할 수 있다.The ethylenically unsaturated urethane oligomer is preferably included in an amount of 1 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content of the ethylenically unsaturated urethane oligomer is less than 1 part by weight, it may be difficult to secure the low refractive properties of the photosensitive resin composition and a problem that the remaining film ratio is deteriorated may occur. problems may arise.
구체적으로 상기 에틸렌성 불포화 우레탄 올리고머는 2 내지 10 개의 관능기, 보다 구체적으로 2 내지 6개의 관능기를 가지며, 아로마틱 구조가 포함되지 않은 구조일 수 있다. 상기 에틸렌성 불포화 우레탄 올리고머는 2개 이상의 관능기를 가져야 상기 감광성 수지 조성물에 광경화 시 막 경화도를 향상시키는 효과가 있으며, 상기 관능기가 11개 이상인 경우 해상도를 저하시키는 문제가 발생할 수 있으며, 상기 관능기가 6개 이하인 경우 접착력 및 해상도를 향상시키는 효과가 특히 우수하게 나타날 수 있다.Specifically, the ethylenically unsaturated urethane oligomer has 2 to 10 functional groups, more specifically 2 to 6 functional groups, and may have a structure that does not include an aromatic structure. The ethylenically unsaturated urethane oligomer has at least two functional groups to have an effect of improving the film curing degree upon photocuring in the photosensitive resin composition, and when the functional group is 11 or more, a problem of lowering resolution may occur, In the case of 6 or less, the effect of improving adhesion and resolution may be particularly excellent.
또한 상기 에틸렌성 불포화 우레탄 올리고머는 하나 이상의 불소 원자를 포함할 수 있다. 상기 에틸렌성 불포화 우렌탄 올리고머에 불소 원자가 포함되는 경우 상기 감광성 수지 조성물의 패턴 형성에 도움을 줄 수 있다.The ethylenically unsaturated urethane oligomer may also contain one or more fluorine atoms. When a fluorine atom is included in the ethylenically unsaturated urethane oligomer, it may help to form a pattern of the photosensitive resin composition.
상기 에틸렌성 불포화 우레탄 올리고머는 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 포함될 수 있다. 상기 에틸렌성 불포화 우레탄 올리고머가 1 중량부 미만으로 포함되는 경우 낮은 감도로 인해 잔막율이 나빠지는 문제가 발생할 수 있으며, 50 중량부를 초과하여 포함되는 경우 현상성이 떨어지고, 해상도가 저하되는 문제가 발생할 수 있다.The ethylenically unsaturated urethane oligomer may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer. When the ethylenically unsaturated urethane oligomer is included in an amount of less than 1 part by weight, a problem that the residual film ratio is deteriorated due to low sensitivity may occur, and when it is included in excess of 50 parts by weight, developability is deteriorated, and a problem of lowering resolution may occur. can
상기 감광성 수지 조성물은 에틸렌성 불포화 다관능 모노머를 더 포함할 수 있으며, 구체적으로 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 에틸렌성 불포화 다관능 모노머를 더 포함할 수 있다. 상기 에틸렌성 불포화 다관능 모노머가 1 중량부 미만으로 포함되는 경우 낮은 감도로 인해 잔막율이 나빠지는 문제가 발생할 수 있으며, 50 중량부를 초과하여 포함되는 경우 현상성이 떨어지고, 해상도가 저하되는 문제가 발생할 수 있다.The photosensitive resin composition may further include an ethylenically unsaturated polyfunctional monomer, and specifically, may further include an ethylenically unsaturated polyfunctional monomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer. When the ethylenically unsaturated polyfunctional monomer is included in an amount of less than 1 part by weight, a problem that the residual film ratio is deteriorated due to low sensitivity may occur, and when it is included in excess of 50 parts by weight, developability is deteriorated and the resolution is lowered. can occur
상기 에틸렌성 불포화 다관능 모노머는 예를 들어 1,4-부탄디올디아크릴레이트, 1,3-부틸렌글리콜디아크릴레이트, 에틸렌글리콜디아크릴레이트, 트리메틸올프로판디아크릴레이트, 트리메틸올프로판트리아크릴레이트, 펜타에리스리톨트리아크릴레이트, 펜타에리스리톨테트라아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 디펜타에리스리톨헥사디아크릴레이트, 디펜타에리스리톨트리디아크릴레이트, 디펜타에리스리톨디아크릴레이트, 솔비톨트리아크릴레이트, 비스페놀 A 디아크릴레이트 유도체, 디펜타아리스리톨폴리아크릴레이트, 및 이들의 메타크릴레이트류, 불소계아크릴레이트, 불소계메타크릴레이트류 등을 사용할 수 있으며, 이들을 단독 또는 2종 이상을 혼합하여 사용할 수 있으나, 상기 예시에 한정되는 것은 아니다. The ethylenically unsaturated polyfunctional monomer is, for example, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate , pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol Triacrylate, bisphenol A diacrylate derivative, dipentaarithritol polyacrylate, and their methacrylates, fluorine-based acrylates, fluorine-based methacrylates, etc. may be used, and these may be used alone or in combination of two or more can be used, but is not limited to the above example.
상기 에틸렌성 불포화 다관능 모노머는 불소를 포함하고 있는 것이 상기 감광성 수지 조성물의 패턴을 형성하는데 유리할 수 있다.It may be advantageous for the ethylenically unsaturated polyfunctional monomer to include fluorine in forming a pattern of the photosensitive resin composition.
상기 용매는 상기 아크릴계 공중합체 100 중량부에 대하여, 10 내지 500 중량부 포함될 수 있으며, 10 중량부 미만인 경우 다른 성분이 용매에 충분히 용해되지 못하는 문제가 발생할 수 있으며, 500 중량부를 초과하는 경우 상기 감광성 수지 조성물이 과도하게 묽게 되어 현상성과 접착력이 떨어지는 문제가 발생할 수 있다.The solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the acrylic copolymer, and if it is less than 10 parts by weight, other components may not be sufficiently dissolved in the solvent, and if it exceeds 500 parts by weight, the photosensitivity Since the resin composition is excessively thin, there may be a problem in that developability and adhesion are deteriorated.
상기 감광성 수지 조성물에 포함되는 용매는 감광성 수지 조성물에 통상적으로 사용 가능한 공지의 용매가 될 수 있으며, 구체적인 예로 프로필렌글리콜모노에틸프로피오네이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜부틸에테르프로피오네이트 등의 프로필렌글리콜알킬에테르아세테이트류; 메탄올, 에탄올 등의 알코올류; 테트라히드로퓨란 등의 에테르류; 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르 아세테이트류; 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜디메틸에테르 등의 디에틸렌글리콜류; 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르 등의 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜부틸에테르아세테이트 등의 프로필렌글리콜알킬에테르아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 메틸에틸케톤, 시클로헥사논, 4-히드록시 4-메틸 2-펜타논 등의 케톤류; 또는 초산메틸, 초산에틸, 초산프로필, 초산부틸, 2-히드록시 프로피온산 에틸, 2-히드록시 2-메틸프로피온산 메틸, 2-히드록시 2-메틸프로피온산 에틸, 히드록시초산메틸, 히드록시초산에틸, 히드록시초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시프로피온산메틸, 3-히드록시프로피온산에틸, 3-히드록시프로피온산프로필, 3-히드록시프로피온산부틸, 2-히드록시 3-메틸부탄산 메틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산프로필, 메톡시초산부틸, 에톡시초산메틸, 에톡시초산에틸, 에톡시초산프로필, 에톡시초산부틸, 프로폭시초산메틸, 프로폭시초산에틸, 프로폭시초산프로필, 프로폭시초산부틸, 부톡시초산메틸, 부톡시초산에틸, 부톡시초산프로필, 부톡시초산부틸, 2-메톡시프로피온산메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산프로필, 2-메톡시프로피온산부틸, 2-에톡시프로피온산메틸, 2-에톡시플피온산에틸, 2-에톡시프로피온산프로필, 2-에톡시프로피온산부틸, 2-부톡시프로피온산메틸, 2-부톡시프로피온산에틸, 2-부톡시프로피오산프로필, 2-부톡시프로피온산부틸, 3-메톡시프로피온산메틸 3-메톡시프로피온산에틸, 3-메톡시프로피온산프로필, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산프로필, 3-에톡시프로피온산부틸, 3-프로폭시프로피온산메틸, 3-프로폭시프로피온산에틸, 3-프로폭시프로피온산프로필, 3-프로폭시프로피온산부틸, 3-부톡시프로피온산메틸, 3-부톡시프로피온산에틸, 3-부톡시프로피온산프로필, 3-부톡시프로피온산부틸 등의 에스테르류 등을 사용할 수 있으며, 이들은 필요에 따라 1종 이상 혼합 사용이 가능하나, 상기 예시에 제한되지 않는다. 상기 용매 예시 중 특히 다른 성분과의 반응성 및 용이한 도포막 형성을 위해서 프로필렌글리콜모노에틸프로피오네이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트 및 프로필렌글리콜부틸에테르프로피오네이트 와 같은 프로필렌글리콜알킬에테르아세테이트류의 용매를 사용할 수 있다.The solvent included in the photosensitive resin composition may be a known solvent that is commonly used in the photosensitive resin composition, and specific examples thereof include propylene glycol monoethyl propionate, propylene glycol methyl ether propionate, and propylene glycol ethyl ether propionate. , propylene glycol alkyl ether acetates such as propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones, such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methylpropionate, 2-hydroxy 2-methylpropionate ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-methyl hydroxypropionate, 3-ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxyl -Methyl butanoate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate , ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-ethoxypropylpropionate, 2-ethoxybutylpropionate, 2-butoxypropionate methyl , 2-butoxypropionate ethyl, 2-butoxypropionate propyl, 2-butoxypropionate butyl, 3-methoxymethylpropionate 3-methoxyethyl propionate, 3-methoxypropionate propyl, 3-ethoxypropionate methyl, 3-ethyl 3-ethoxypropionate, 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate ethyl, 3-propoxypropionate propyl, 3-propoxypropionate butyl, 3 -Esters such as methyl butoxypropionate, 3-butoxypropionate ethyl, 3-butoxypropionate propyl, 3-butoxypropionate butyl, etc. may be used, and one or more of these may be mixed and used as needed. Examples are not limited. Among the examples of the solvent, propylene glycol monoethyl propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and A solvent of propylene glycol alkyl ether acetate such as propylene glycol butyl ether propionate can be used.
상기 감광성 수지 조성물은 해상도 향상을 위하여 UV(Ultraviolet rays) 흡수제를 더 포함할 수 있다. 상기 UV 흡수제는 예를 들어 벤조페논류, 트라이진류, 벤조트리아졸류, 옥사닐리드류 등을 사용할 수 있으나, 상기 예시에 제한되지 않는다. 상기 UV 흡수제의 함량은 상기 아크릴계 공중합체 100 중량부에 대하여 0.5 내지 5 중량부로 사용하는 것이 상기 해상도 향상에 도움이 될 수 있다.The photosensitive resin composition may further include a UV (Ultraviolet Rays) absorber to improve resolution. The UV absorber may include, for example, benzophenones, trigins, benzotriazoles, oxanilides, and the like, but is not limited to the above examples. The content of the UV absorber may be helpful in improving the resolution if used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer.
상기 감광성 수지 조성물은 하부 기판과의 접착력 향상을 위하여 실란 커플링제를 더 포함할 수 있다. 상기 실란 커플링제는 예를 들어 (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시크로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시크로헥실)에틸트리에톡시실레인, 아미노프로필트리메톡시실레인, 아미노프로필트리에톡시실레인, 3-트리에톡시실리-N-(1,3 디메틸-부틸리덴)프로필아민, N-2(아미노에틸)3-아미노프로필트리메톡시실레인, N-2(아미노에틸)3-아미노프로필트리에톡시실레인, N-2(아미노에틸)3-아미노프로필메틸디메톡시실레인, N-페닐-3-아미노프로필트리메톡시실레인 또는 (3-이소시아네이트프로필)트리에톡시실레인 등을 단독 또는 2종 이상 혼합하여 사용할 수 있으나, 상기 예시에 한정되지 않는다. 상기 실란 커플링제는 상기 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 10 중량부로 사용하는 것이 상기 접착력 향상에 도움이 될 수 있다.The photosensitive resin composition may further include a silane coupling agent to improve adhesion to the lower substrate. The silane coupling agent is, for example, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane Phosphorus, 2- (3,4-epoxy cyclohexyl) ethyl trimethoxysilane, 2- (3,4-epoxy cyclohexyl) ethyl triethoxy silane, aminopropyl trimethoxysilane, aminopropyl Triethoxysilane, 3-triethoxysilyl-N-(1,3 dimethyl-butylidene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(amino Ethyl)3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or (3-isocyanatepropyl)tri Ethoxysilane and the like may be used alone or in combination of two or more, but is not limited to the above examples. The use of the silane coupling agent in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer may help improve the adhesion.
상기 감광성 수지 조성물은 내열성, 내화학성 및 접착력 향상을 위하여 가교제, 구체적으로 멜라민 가교제를 더 포함할 수 있다. 상기 멜라민 가교제로는 예를들어 요소와 포름알데히드의 축합생성물, 멜라민과 포름알데히드의 축합생성물, 또는 알코올로부터 얻어진 메틸올요소알킬에테르류나 메틸올멜라민알킬에테르류 등을 사용할 수 있으며, 구체적으로 상기 요소와 포름알데히드의 축합생성물로는 모노메틸올요소, 디메틸올요소 등을 사용할 수 있다. 상기 멜라민과 포름알데히드의 축합생성물로는 헥사메틸올멜라민을 사용할 수 있으며, 그밖에 멜라민과 포름알데히드의 부분적인 축합생성물도 사용할 수 있다. 또한 상기 메틸올요소알킬에테르류로는 요소와 포름알데히드의 축합생성물에 메틸올기의 부분 또는 전부에 알코올올류를 반응시켜 얻어지는 것으로, 그 구체적 예로는 모노메틸요소메틸에테르, 디메틸요소메틸에테르 등을 사용할 수 있다. 상기 메틸올멜라민알킬에테르류로는 멜라민과 포름알데히드의 축합생성물에 메틸올기의 부분 또는 전부에 알코올류를 반응시켜 얻어지는 것으로, 그 구체적 예로서는 헥사메틸올멜라민헥사메틸에테르, 헥사메틸올멜라인헥사부틸에테르 등을 사용할 수 있다. 또한, 멜라민의 아미노기의 수소원자가 히드록시 메틸기 및 메톡시 메틸기로 치환된 구조의 화합물, 멜라민의 아미노기의 수소원자가 부톡시 메틸기 및 메톡시 메틸기로 치환된 구조의 화합물 등도 사용할 수 있으며, 특히 메틸올멜라민알킬에테르류를 사용하는 것이 바람직하다. 상기 멜라닌 가교제는 상기 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 10 중량부로 사용하는 것이 상기 내열성, 내화학성 및 접착력 향상에 도움이 될 수 있다.The photosensitive resin composition may further include a crosslinking agent, specifically a melamine crosslinking agent, to improve heat resistance, chemical resistance, and adhesion. As the melamine crosslinking agent, for example, a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, or methylol urea alkyl ethers or methylol melamine alkyl ethers obtained from alcohol may be used, and specifically, the urea Monomethylol urea, dimethylol urea, etc. can be used as a condensation product of formaldehyde and As the condensation product of melamine and formaldehyde, hexamethylolmelamine may be used, and in addition, a partial condensation product of melamine and formaldehyde may be used. In addition, as the methylol urea alkyl ethers, a condensation product of urea and formaldehyde is obtained by reacting part or all of the methylol groups with alcohols, and specific examples thereof include monomethyl urea methyl ether and dimethyl urea methyl ether. can The methylol melamine alkyl ethers are those obtained by reacting a part or all of methylol groups with alcohols in a condensation product of melamine and formaldehyde, and specific examples thereof include hexamethylolmelamine hexamethyl ether, hexamethylol melamine hexabutyl Ether and the like can be used. In addition, a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with a hydroxymethyl group and a methoxymethyl group, a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with a butoxymethyl group and a methoxymethyl group, etc. can also be used, especially methylolmelamine It is preferable to use alkyl ethers. Using the melanin crosslinking agent in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer may help to improve the heat resistance, chemical resistance and adhesion.
상기 감광성 수지 조성물은 도포성 및 현상성을 향상시키기 위해 계면 활성제를 포함할 수 있으며, 구체적으로 불소계 계면활성제 및 실리콘 계면활성제 중 하나 이상을 포함할 수 있다. 상기 계면활성제는 상기 감광성 수지 조성물에서 용매를 제외한 고형분 100 중량부에 대하여 0.0001 내지 2 중량부로 사용하는 것이 상기 도포성 및 현상성 개선을 위해 바람직하다.The photosensitive resin composition may include a surfactant to improve coatability and developability, and specifically may include at least one of a fluorine-based surfactant and a silicone surfactant. The surfactant is preferably used in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the solid content excluding the solvent in the photosensitive resin composition to improve the applicability and developability.
상기 네가티브 감광성 수지 조성물 중 고형분은 10 내지 50 중량% 일 수 있으며, 상기 범위를 벗어나면 2 내지 4㎛ 두께의 박막을 형성하는 데 문제가 있을 수 있다.The solid content of the negative photosensitive resin composition may be 10 to 50 wt %, and if it is out of the above range, there may be a problem in forming a thin film having a thickness of 2 to 4 μm.
본 발명의 일 실시예에 따른 표시장치는 상기 네가티브 감광성 수지 조성물의 경화체를 포함하는 표시장치이며, 구체적으로 상기 조성물의 경화체는 표시장치의 광학부재, 예를 들어 층간 절연막에 포함되어 사용될 수 있다. A display device according to an embodiment of the present invention is a display device including a cured body of the negative photosensitive resin composition, and specifically, the cured body of the composition may be included in an optical member of the display device, for example, an interlayer insulating film.
상기 표시장치는 1.5 이하의 굴절률을 가진 광학부재를 포함하며, 상기 광학부재는 상기 경화체를 포함할 수 있다.The display device may include an optical member having a refractive index of 1.5 or less, and the optical member may include the curing body.
상기 네가티브 감광성 수지 조성물을 이용하여 절연막을 형상하는 방법의 일예는 다음과 같다. 먼저 본 발명의 저굴절 네가티브 감광성 수지 조성물을 스프레이법, 슬릿코터법, 롤코터법, 회전도포법 등으로 기판 표면에 도포하고, 프리베이크에 의해 용매를 제거하여 도포막을 형성한다. 이때, 상기 열처리는 80 내지 100 ℃의 온도에서 1 내지 5 분간 실시하는 것이 바람직하다. 그 다음, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 엑스선 등을 상기 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다. 상기 현상액은 알칼리 수용액을 사용하는 것이 좋으며, 구체적으로 수산화나트륨, 수산화칼륨, 탄산나트륨 등의 무기 알칼리류; n-프로필아민 등의 1급 아민류; 디에틸아민, n-프로필아민 등의 2급 아민류; 트리메틸아민, 메틸디에틸아민, 디메틸에틸아민, 트리에틸아민 등의 3급 아민류; 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올아민 등의 알콜아민류; 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액 등을 사용할 수 있다. 이때, 상기 현상액은 알칼리성 화합물을 0.01 내지 10 중량%의 농도로 용해시켜 사용되며, 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가할 수도 있다. 또한, 상기와 같은 현상액으로 현상한 후 초순수로 50 내지 180 초간 세정하여 불필요한 부분을 제거하고 건조하여 패턴을 형성하고, 선택적으로 상기 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 80 내지 150 ℃의 온도에서 30 내지 180 분간 큐어링하여 최종 층간 절연막을 얻을 수 있다.An example of a method of forming an insulating film using the negative photosensitive resin composition is as follows. First, the low refractive index negative photosensitive resin composition of the present invention is applied to the surface of a substrate by a spray method, a slit coater method, a roll coater method, a rotation coating method, etc., and the solvent is removed by prebaking to form a coating film. At this time, the heat treatment is preferably performed at a temperature of 80 to 100 ℃ 1 to 5 minutes. Then, a predetermined pattern is formed by irradiating visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc. to the formed coating film according to a previously prepared pattern, and developing it with a developer to remove unnecessary parts. It is preferable to use an aqueous alkali solution as the developer, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate; primary amines such as n-propylamine; secondary amines such as diethylamine and n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; Alternatively, an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving an alkaline compound at a concentration of 0.01 to 10 wt%, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added. In addition, after developing with the developer as described above, washing with ultrapure water for 50 to 180 seconds to remove unnecessary parts and drying to form a pattern, selectively irradiating light such as ultraviolet rays to the formed pattern, and heating the pattern in an oven, etc. A final interlayer insulating film can be obtained by curing the device at a temperature of 80 to 150° C. for 30 to 180 minutes.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[제조예: 네가티브 감광성 수지 조성물 제조][Preparation Example: Preparation of negative photosensitive resin composition]
실시예 1Example 1
(아크릴계 공중합체 제조)(Manufacture of acrylic copolymer)
냉각관과 교반기를 구비한 플라스크에 공중합되는 단량체인 하기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 하기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 넣고, 추가적으로 2,2'-아조비스(2,4-디메틸발레로니트릴) 8 중량부, 테트라하이드로퓨란 400 중량부를 넣어, 질소 치환한 후 완만하게 교반하였다. 상기 반응 용액을 55℃까지 승온시켜 48시간 동안 이 온도를 유지한다. 반응이 완료된 아크릴계 공중합체를 상온(23℃)으로 냉각시킨 후 프로필렌글리콜 모노메틸에테르아세테이트 200 중량부를 넣고 감압 증류를 진행한다. GC(Gas Chromatography) 분석을 통하여 테트라하이드로퓨란 함량이 0.5 중량% 이하일 때 감압 증류를 종료한다. 고형분 농도가 30 중량%가 되도록 추가적으로 프로필렌글리콜 모노메틸에테르아세테이트를 넣는다. 중합체의 중량평균분자량은 5,000인 중합체 용액을 제조하였다. 이때, 중량평균분자량은 GPC(Gel Permeation Chromatography)를 사용하여 측정한 폴리스티렌 환산평균분자량이다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by the following formula (1), which is a monomer copolymerized in a flask equipped with a cooling tube and a stirrer, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in the following formula (4), methacryl 30 parts by weight of acid and 40 parts by weight of styrene were added, and 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 400 parts by weight of tetrahydrofuran were added, followed by nitrogen substitution, followed by gentle stirring. The reaction solution was heated to 55° C. and maintained at this temperature for 48 hours. After the reaction was completed, the acrylic copolymer was cooled to room temperature (23° C.), and 200 parts by weight of propylene glycol monomethyl ether acetate was added thereto, followed by distillation under reduced pressure. When the tetrahydrofuran content is 0.5 wt % or less through GC (Gas Chromatography) analysis, vacuum distillation is terminated. Further, propylene glycol monomethyl ether acetate is added so that the solid content concentration is 30% by weight. A polymer solution having a weight average molecular weight of the polymer of 5,000 was prepared. In this case, the weight average molecular weight is a polystyrene reduced average molecular weight measured using GPC (Gel Permeation Chromatography).
(네가티브 감광성 수지 조성물) (Negative photosensitive resin composition)
상기 제조한 아크릴계 공중합체를 포함하는 중합체 용액 100 중량부, 광개시제로는 2-(O-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온 15 중량부, 불소계 에틸렌성 불포화 우레탄 올리고머로는 신아티엔씨사의 SFA-420 10 중량부, 에틸렌성 불포화 화합물로는 디펜타에리스리톨헥사디아크릴레이트 10 중량부, 이온개시제로는 4-메틸페닐(4-(2-메틸프로필페닐))요오드늄육불화인 1 중량부, UV 흡수제로는 2,4-비스(2-하이드록시-4-부톡시페닐l)-6-(2,4-디부톡시페닐)-1,3,5-트라아진 1 중량부, 실란 커플링제로는 (3-이소시아네이트프로필)트리에톡시실레인 1 중량부, 실리콘계 계면활성제 1 중량부, 멜라민 가교제 1 중량부를 혼합하였다. 상기 혼합물의 고형분 함량이 20 내지 30 중량부가 되도록 프로필렌글리콜모노에틸아세테이트 추가하여 용해시킨 후, 0.2㎛의 밀리포아필터로 여과하여 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.100 parts by weight of the polymer solution containing the prepared acrylic copolymer, 15 parts by weight of 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione as a photoinitiator, fluorine-based As an ethylenically unsaturated urethane oligomer, 10 parts by weight of SFA-420 manufactured by Shin A&C Co., Ltd., 10 parts by weight of dipentaerythritol hexadiacrylate as an ethylenically unsaturated compound, and 4-methylphenyl (4-(2-methylpropylphenyl) as an ion initiator )) 1 part by weight of phosphorus iodonium hexafluoride, 2,4-bis(2-hydroxy-4-butoxyphenyl l)-6-(2,4-dibutoxyphenyl)-1,3,5 as UV absorber - 1 part by weight of triazine, 1 part by weight of (3-isocyanatepropyl)triethoxysilane as a silane coupling agent, 1 part by weight of a silicone-based surfactant, and 1 part by weight of a melamine crosslinking agent were mixed. After adding and dissolving propylene glycol monoethyl acetate so that the solid content of the mixture was 20 to 30 parts by weight, it was filtered through a 0.2 μm Millipore filter to prepare a coating solution for a negative photosensitive resin composition.
[화학식 1][Formula 1]
Figure PCTKR2021018681-appb-img-000013
Figure PCTKR2021018681-appb-img-000013
[화학식 4][Formula 4]
Figure PCTKR2021018681-appb-img-000014
Figure PCTKR2021018681-appb-img-000014
상기 화학식 4에서 n은 0 내지 9의 정수In Formula 4, n is an integer of 0 to 9
실시예 2 Example 2
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 5 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 5 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 3 Example 3
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 10 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 10 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 4 Example 4
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 in the total monomers, and 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene A coating solution of a negative photosensitive resin composition was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts by weight was applied.
실시예 5 Example 5
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 30 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 30 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 6 Example 6
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 7 Example 7
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 하기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in the following Formula 5, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
[화학식 5][Formula 5]
Figure PCTKR2021018681-appb-img-000015
Figure PCTKR2021018681-appb-img-000015
상기 화학식 5에서 n은 1 내지 10의 정수In Formula 5, n is an integer of 1 to 10
실시예 8 Example 8
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 5 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 5 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 9 Example 9
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 10 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 10 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 10 Example 10
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 11 Example 11
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 30 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 30 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 12 Example 12
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 13 Example 13
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 하기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in the following Formula 6, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
[화학식 6][Formula 6]
Figure PCTKR2021018681-appb-img-000016
Figure PCTKR2021018681-appb-img-000016
상기 화학식 6에서 n은 0 내지 9의 정수In Formula 6, n is an integer of 0 to 9
실시예 14 Example 14
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 5 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 5 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 15 Example 15
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 10 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 10 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 16 Example 16
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 17 Example 17
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 30 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 30 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 18 Example 18
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 19 Example 19
전체 총 단량체 중 하기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2 below among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
[화학식 2][Formula 2]
Figure PCTKR2021018681-appb-img-000017
Figure PCTKR2021018681-appb-img-000017
상기 화학식 2에서 n은 1 내지 10의 정수In Formula 2, n is an integer of 1 to 10
실시예 20 Example 20
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 21 Example 21
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 5, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 22 Example 22
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 6, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 23 Example 23
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 24 Example 24
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 25 Example 25
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 26 Example 26
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 27 Example 27
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 30 parts by weight of styrene was applied.
실시예 28 Example 28
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 29 Example 29
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 5 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 30 Example 30
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Chemical Formula 2 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 31 Example 31
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 32 Example 32
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 5 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 33 Example 33
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 34 Example 34
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 35 Example 35
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 36 Example 36
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 37 Example 37
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 38 Example 38
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 39 Example 39
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 40 Example 40
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 41 Example 41
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 42 Example 42
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 43 Example 43
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 2 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in the Chemical Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 44 Example 44
전체 총 단량체 중 하기 화학식 3으로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of the epoxy group-containing unsaturated compound represented by the following Chemical Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Chemical Formula 4, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
[화학식 3][Formula 3]
Figure PCTKR2021018681-appb-img-000018
Figure PCTKR2021018681-appb-img-000018
상기 화학식 R은 C수 0~10의 정수로 알킬, 알켄, 알릴 구조의 유기기 화합물The formula R is an organic compound having an alkyl, alkene, or allyl structure as an integer of 0 to 10 C
실시예 45 Example 45
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 46 Example 46
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 47 Example 47
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 6, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 48 Example 48
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Chemical Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 49 Example 49
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, 20 parts by weight of a fluorinated unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 50 Example 50
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 51 Example 51
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 52 Example 52
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 53 Example 53
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 54 Example 54
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 5 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 55 Example 55
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 5 in Formula 3, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 56 Example 56
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 57 Example 57
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 58 Example 58
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer where n is 5 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 59 Example 59
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 60 Example 60
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 61 Example 61
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 5, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 62 Example 62
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 63 Example 63
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 64 Example 64
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 40 parts by weight of parts and styrene was applied.
실시예 65 Example 65
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 66 Example 66
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 5, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 67 Example 67
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 6, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 for the remainder of applying an acrylic copolymer copolymerized with parts and 30 parts by weight of styrene.
실시예 68 Example 68
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 69 Example 69
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 1인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 1 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 70 Example 70
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 3인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 3 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 71 Example 71
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 5인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 5 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 72 Example 72
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 9인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 9 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 73 Example 73
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 1인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 1 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 74 Example 74
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 3인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 3 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 75 Example 75
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 5인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 5 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 76 Example 76
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 9인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 9 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 77 Example 77
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 1인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 1 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 78 Example 78
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 3인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 3 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 79 Example 79
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 5인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 5 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 80 Example 80
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 9인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 9 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 81 Example 81
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 82 Example 82
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 41 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 83 Example 83
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 1 중량부, 메타크릴산 30 중량부, 스티렌 49 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 1 part by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 49 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 84 Example 84
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 4 중량부, 메타크릴산 30 중량부, 스티렌 46 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 4 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 46 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 85 Example 85
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 31 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 31 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 86 Example 86
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 40 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 40 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 87 Example 87
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 50 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 50 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 88 Example 88
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 89 Example 89
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 90 Example 90
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 91 Example 91
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 92 Example 92
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 41 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 93 Example 93
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 1 중량부, 메타크릴산 30 중량부, 스티렌 49 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 1 part by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 49 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 94 Example 94
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 4 중량부, 메타크릴산 30 중량부, 스티렌 46 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 4 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 46 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 95 Example 95
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 31 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 31 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 96 Example 96
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 40 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 40 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 97 Example 97
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 50 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 50 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 98 Example 98
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 99 Example 99
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 100 Example 100
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 5, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 101 Example 101
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 45 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 102 Example 102
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 41 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 103 Example 103
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 1 중량부, 메타크릴산 30 중량부, 스티렌 49 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 1 part by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 49 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 104 Example 104
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 4 중량부, 메타크릴산 30 중량부, 스티렌 46 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 4 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 46 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 105 Example 105
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 31 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 31 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 106 Example 106
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 40 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 40 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 107 Example 107
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 50 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 50 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 108 Example 108
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 19 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 109 Example 109
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 110 Example 110
전체 총 단량체 중 상기 화학식 1으로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the copolymerized acrylic copolymer was applied.
실시예 111 Example 111
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 1 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 112 Example 112
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 113 Example 113
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 114 Example 114
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 115 Example 115
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 116 Example 116
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 3 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 117 Example 117
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 118 Example 118
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 119 Example 119
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 120 Example 120
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 10 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 121 Example 121
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 122 Example 122
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 123 Example 123
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 124 Example 124
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorinated unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 125 Example 125
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 126 Example 126
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 127 Example 127
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 128 Example 128
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 129 Example 129
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 130 Example 130
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 131 Example 131
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 132 Example 132
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer where n is 9 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 133 Example 133
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Formula 2, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 134 Example 134
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 135 Example 135
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 2 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 10 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 136 Example 136
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 137 Example 137
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 138 Example 138
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 139 Example 139
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 140 Example 140
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 1 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 141 Example 141
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 142 Example 142
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 143 Example 143
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 144 Example 144
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 145 Example 145
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 146 Example 146
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 147 Example 147
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 148 Example 148
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 5 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 149 Example 149
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 150Example 150
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer in which n is 5 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 10 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 151 Example 151
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 152 Example 152
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 7 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 153 Example 153
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 154 Example 154
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, and 30 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 155 Example 155
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 10 parts by weight of methacrylic acid among the total monomers A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 156 Example 156
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 5 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 45 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 5 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 45 parts by weight and styrene was applied.
실시예 157Example 157
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 9 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 41 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 9 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Formula 3 among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing parts and 41 parts by weight of styrene was applied.
실시예 158Example 158
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 31 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 19 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 31 parts by weight of the epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 3, among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 19 parts by weight and 19 parts by weight of styrene was applied.
실시예 159Example 159
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, and 30 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerizing 10 parts by weight and 10 parts by weight of styrene was applied.
실시예 160Example 160
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of the epoxy group-containing unsaturated compound represented by an integer in which n is 9 in Chemical Formula 3 among the total monomers, 20 parts by weight of the fluorine-based unsaturated compound represented by an integer in which n is 7 in Chemical Formula 4, and 10 parts by weight of methacrylic acid A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that an acrylic copolymer obtained by copolymerization of 20 parts by weight and 20 parts by weight of styrene was applied.
실시예 161Example 161
전체 총 단량체 중 글리시딜 메타크릴레이트 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 162Example 162
전체 총 단량체 중 글리시딜 메타크릴레이트 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 163Example 163
전체 총 단량체 중 글리시딜 메타크릴레이트 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 164Example 164
전체 총 단량체 중 글리시딜 메타크릴레이트 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 165Example 165
전체 총 단량체 중 글리시딜 메타크릴레이트 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 166Example 166
전체 총 단량체 중 글리시딜 메타크릴레이트 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer where n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 167Example 167
전체 총 단량체 중 글리시딜 메타크릴레이트 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of glycidyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer of 7 in Formula 4, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene After applying the coalescence, a negative photosensitive resin composition coating solution similar to Example 1 was prepared.
실시예 168Example 168
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 10 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 40 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 10 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 40 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 169Example 169
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 20 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 170Example 170
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 20 중량부에 대하여, 상기 화학식 5에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 5, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 171Example 171
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 20 중량부에 대하여, 상기 화학식 6에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 30 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorinated unsaturated compound represented by an integer in which n is 7 in Formula 6, 30 parts by weight of methacrylic acid, and 30 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 172Example 172
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 30 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 30 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 173Example 173
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 40 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 30 중량부, 스티렌 10 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 40 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 30 parts by weight of methacrylic acid, and 10 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 174Example 174
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 50 중량부에 대하여, 상기 화학식 4에서 n이 7인 정수로 표시되는 불소계 불포화 화합물 20 중량부, 메타크릴산 10 중량부, 스티렌 20 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 50 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, 20 parts by weight of a fluorine-based unsaturated compound represented by an integer in which n is 7 in Formula 4, 10 parts by weight of methacrylic acid, and 20 parts by weight of styrene A negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the acrylic copolymer obtained by copolymerization was applied.
실시예 175Example 175
실시예 4와 동일한 네가티브 감광성 수지 조성물에서 불소계 에틸렌성 불포화 우레탄 올리고머로는 제외한 코팅 용액을 제조하였다.In the same negative photosensitive resin composition as in Example 4, a coating solution was prepared except for the fluorine-based ethylenically unsaturated urethane oligomer.
실시예 176Example 176
실시예 4와 동일한 네가티브 감광성 수지 조성물에서 이온 개시제를 제외한 코팅 용액을 제조하였다.A coating solution was prepared except for the ion initiator in the same negative photosensitive resin composition as in Example 4.
실시예 177Example 177
실시예 4와 동일한 네가티브 감광성 수지 조성물에서 UV 흡수제를 제외한 코팅 용액을 제조하였다.A coating solution was prepared except for the UV absorber in the same negative photosensitive resin composition as in Example 4.
비교예 1Comparative Example 1
전체 총 단량체 중 상기 화학식 1로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.An acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of the epoxy group-containing unsaturated compound represented by Formula 1 among the total monomers was applied, and the remainder was the same as in Example 1 Negative photosensitive resin composition A coating solution was prepared.
비교예 2Comparative Example 2
전체 총 단량체 중 상기 화학식 2에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 1 in Formula 2 is applied, and the remainder is Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 3Comparative Example 3
전체 총 단량체 중 상기 화학식 2에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 2 above, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 4Comparative Example 4
전체 총 단량체 중 상기 화학식 2에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 5 in Formula 2 is applied, and the remainder is Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 5Comparative Example 5
전체 총 단량체 중 상기 화학식 2에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 2 above, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 6Comparative Example 6
전체 총 단량체 중 상기 화학식 2에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 9 in Formula 2 above, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 7Comparative Example 7
전체 총 단량체 중 상기 화학식 3에서 n이 1인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 1 in Formula 3 is applied, and the remainder is Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 8Comparative Example 8
전체 총 단량체 중 상기 화학식 3에서 n이 3인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 3 in Formula 3, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 9Comparative Example 9
전체 총 단량체 중 상기 화학식 3에서 n이 5인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene with respect to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 5 in Formula 3 is applied, and the remainder is Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 10Comparative Example 10
전체 총 단량체 중 상기 화학식 3에서 n이 7인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer of 7 in Formula 3, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 11Comparative Example 11
전체 총 단량체 중 상기 화학식 3에서 n이 9인 정수로 표시되는 에폭시기 함유 불포화 화합물 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Of the total monomers, an acrylic copolymer obtained by copolymerization of 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied to 20 parts by weight of an epoxy group-containing unsaturated compound represented by an integer where n is 9 in Formula 3, and the remainder was Example 1 The same negative photosensitive resin composition coating solution was prepared.
비교예 12Comparative Example 12
전체 총 단량체 중 글리시딜 메타크릴레이트 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다.Based on 20 parts by weight of glycidyl methacrylate among the total monomers, an acrylic copolymer obtained by copolymerizing 30 parts by weight of methacrylic acid and 50 parts by weight of styrene was applied, and the remainder was the same as in Example 1 to prepare a coating solution for a negative photosensitive resin composition did
비교예 13Comparative Example 13
전체 총 단량체 중 3,4-에폭시사이클로헥실메틸 메타크릴레이트 20 중량부에 대하여, 메타크릴산 30 중량부, 스티렌 50 중량부를 공중합 시킨 아크릴계 공중합체를 적용하고 나머지는 실시예 1과 동일한 네가티브 감광성 수지 조성물 코팅 용액을 제조하였다. Based on 20 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate among the total monomers, an acrylic copolymer obtained by copolymerization of 30 parts by weight of methacrylic acid and 50 parts by weight of styrene is applied, and the remainder is the same negative photosensitive resin as in Example 1. A composition coating solution was prepared.
[실험예: 네가티브 감광성 수지조성물의 물성 평가][Experimental Example: Evaluation of Physical Properties of Negative Photosensitive Resin Composition]
상기 실시예 1 내지 177 및 비교예 1 내지 13에서 공중합 시킨 아크릴 공중합체 및 이를 이용하여 제조된 네가티브 감광성 수지 조성물 코팅 용액을 이용하여 하기와 같은 방법으로 물성을 평가한 후, 그 결과를 하기 표 1 내지 표 10에 나타내었다.The acrylic copolymer copolymerized in Examples 1 to 177 and Comparative Examples 1 to 13 and the negative photosensitive resin composition coating solution prepared using the same were evaluated for physical properties in the following manner, and the results are shown in Table 1 to Table 10.
가) 굴절률 - 실리콘 웨이퍼(Si Wafer) 기판 상부에 스핀코터를 사용하여 상기 실시예 1내지 177 및 비교예 1 내지 13에서 제조된 네가티브 감광성 수지 조성물을 도포한 뒤, 85℃로 120초간 핫 플레이트 상에서 프리베이크하여 2㎛막을 형성하였다. 상기 코팅 된 막에 Canon 노광기 MPA-600으로 200mW/㎠ Intensity 조건에서 각 시료의 감도(Eop)에 해당되는 노광량으로 노광하였다. 이후 최종 경화를 위하여 오븐속에서 85℃로 120분간 가열하여 굴절률 측정용 기판을 얻었다. 굴절률 측정 장비 엘립소미터를 이용하여 굴절률을 측정한다.A) Refractive Index - After applying the negative photosensitive resin composition prepared in Examples 1 to 177 and Comparative Examples 1 to 13 using a spin coater on the upper portion of the silicon wafer (Si Wafer) substrate, on a hot plate at 85° C. for 120 seconds A 2 mu m film was formed by prebaking. The coated film was exposed with an exposure dose corresponding to the sensitivity (Eop) of each sample at 200 mW/cm 2 intensity condition with Canon exposure machine MPA-600. Thereafter, for final curing, the substrate was heated at 85° C. for 120 minutes in an oven to obtain a substrate for measuring refractive index. Measure the refractive index using an ellipsometer.
굴절률이 1.46 이하인 경우를 ◎, 1.46 초과 1.50 미만인 경우를 ○, 1.50 초과 1.55 미만인 경우를 △, 1.55 이상인 경우를 Ｘ로 나타낸다.The case where the refractive index is 1.46 or less is denoted by ◎, the case where the refractive index is more than 1.46 and less than 1.50 is denoted by ○, the case where the refractive index is more than 1.50 and less than 1.55 is denoted by Δ, and the case where it is 1.55 or more is denoted by X.
나) 감도 - 실리콘 웨이퍼(Si Wafer) 기판 상부에 스핀코터를 사용하여 상기 실시예 1 내지 177 및 비교예 1 내지 13에서 제조된 네가티브 감광성 수지 조성물 용액을 도포한 뒤, 85℃로 120초간 핫 플레이트 상에서 프리베이크하여 2㎛막을 형성하였다. 상기에서 얻어진 막에 소정 패턴 마스크(pattern mask)를 사용하여 Canon 노광기 MPA-600으로 200mW/㎠ Intensity 조건에서 5mJ 간격으로 노광량을 split하여 노광하였다. 이후, 테트라메틸암모늄하이드록사이드 2.38 중량%의 수용액으로 23℃에서 60초간 현상한 후, 정제수(DI water)로 60초간 세정하였다. 최종 경화를 위하여 오븐속에서 85℃로 120분간 가열하여 패턴 막을 얻었다. 두께 측정 장비(Nanospec)를 이용하여 두께를 측정하여 두께가 Saturation되는 노광량을 기준으로 감도를 측정한다.B) Sensitivity - After applying the negative photosensitive resin composition solution prepared in Examples 1 to 177 and Comparative Examples 1 to 13 using a spin coater on the top of the silicon wafer (Si Wafer) substrate, a hot plate at 85° C. for 120 seconds A 2 μm film was formed by pre-baking on the top. The film obtained above was exposed by splitting the exposure amount at intervals of 5 mJ at 200 mW/cm 2 Intensity condition with Canon exposure machine MPA-600 using a predetermined pattern mask. Then, after development at 23° C. for 60 seconds with an aqueous solution of 2.38 wt% of tetramethylammonium hydroxide, the mixture was washed with purified water (DI water) for 60 seconds. For final curing, it was heated in an oven at 85° C. for 120 minutes to obtain a patterned film. The thickness is measured using a thickness measuring device (Nanospec), and the sensitivity is measured based on the exposure amount at which the thickness is saturated.
다) 해상도 - 실리콘 웨이퍼(Si Wafer) 기판 상에 스핀코터를 사용하여 상기 실시예 1 내지 177 및 비교예 1 내지 13에서 제조된 네가티브 감광성 수지 조성물 용액을 도포한 뒤, 85℃로 120초간 핫 플레이트 상에서 프리베이크하여 2.0㎛막을 형성하였다. 상기에서 얻어진 막에 소정 패턴 마스크(pattern mask)를 사용하여 Canon 노광기 MPA-600로 200mW/㎠ Intensity 조건에서 각 시료의 감도(Eop)에 해당되는 노광량으로 노광하였다. 이후, 테트라메틸암모늄하이드록사이드 2.38 중량%의 수용액으로 23℃에서 60초간 현상한 후, 정제수(DI water)로 60초간 세정하였다. 최종 경화를 위하여 오븐속에서 85℃로 120분간 가열하여 패턴 막을 얻었다. SEM을 이용하여 10㎛ Hole CD의 패턴 프로파일(Profile)을 측정한다. C) Resolution - After applying the negative photosensitive resin composition solution prepared in Examples 1 to 177 and Comparative Examples 1 to 13 using a spin coater on a silicon wafer (Si Wafer) substrate, a hot plate at 85° C. for 120 seconds A 2.0 μm film was formed by pre-baking on the top. Using a predetermined pattern mask, the film obtained above was exposed with an exposure dose corresponding to the sensitivity (Eop) of each sample under 200 mW/cm 2 Intensity condition with a Canon exposure machine MPA-600. Then, after development at 23° C. for 60 seconds with an aqueous solution of 2.38 wt% of tetramethylammonium hydroxide, the mixture was washed with purified water (DI water) for 60 seconds. For final curing, it was heated in an oven at 85° C. for 120 minutes to obtain a patterned film. Measure the pattern profile of 10㎛ Hole CD using SEM.
CD bias가 1㎛ 이하 일 경우 ◎, CD bias가 1㎛ 초과 2㎛ 이하 일 경우 ○, CD bias가 2㎛ 초과 4㎛ 이하 일 경우 △, 4㎛ 초과 일 경우 Ｘ로 표시하였다.When the CD bias was less than 1㎛, ◎, when the CD bias was more than 1㎛ and less than 2㎛, ○, when the CD bias was more than 2㎛ and less than 4㎛, △, and when it was more than 4㎛, X.
라) 접착력 - SiNx 기판 상에 스핀코터를 사용하여 상기 실시예 1 내지 80 및 비교예 1 내지 110에서 제조된 네가티브 감광성 수지 조성물 용액을 도포한 뒤, 85℃로 120초간 핫 플레이트 상에서 프리베이크하여 2.0㎛막을 형성하였다. 상기 코팅 된 막에 Canon 노광기 MPA-600으로 200mW/㎠ Intensity 조건에서 각 시료의 감도(Eop)에 해당되는 노광량으로 노광하였다. 이후 최종 경화를 위하여 오븐속에서 85℃로 120분간 가열하여 접착력 측정용 기판을 얻었다. Cross cut Adhesion test(ASTM D3359)로 접착력을 평가하였다.D) Adhesion - After applying the negative photosensitive resin composition solution prepared in Examples 1 to 80 and Comparative Examples 1 to 110 using a spin coater on the SiNx substrate, pre-baked on a hot plate at 85° C. for 120 seconds to 2.0 A mu m film was formed. The coated film was exposed with an exposure dose corresponding to the sensitivity (Eop) of each sample at 200 mW/cm 2 intensity condition with Canon exposure machine MPA-600. Then, for final curing, it was heated at 85° C. for 120 minutes in an oven to obtain a substrate for measuring adhesion. Adhesion was evaluated by cross cut Adhesion test (ASTM D3359).
ASTM D3359 평가 결과 5B일 경우 ◎, 3B~4B일 경우 ○, 1B~2B일 경우 △, 0B일 경우 Ｘ로 표시하였다.As a result of ASTM D3359 evaluation, 5B was indicated by ◎, 3B to 4B was indicated by ○, 1B to 2B was indicated by △, and 0B was indicated by X.
Figure PCTKR2021018681-appb-img-000019
Figure PCTKR2021018681-appb-img-000019
Figure PCTKR2021018681-appb-img-000020
Figure PCTKR2021018681-appb-img-000020
Figure PCTKR2021018681-appb-img-000021
Figure PCTKR2021018681-appb-img-000021
Figure PCTKR2021018681-appb-img-000022
Figure PCTKR2021018681-appb-img-000022
Figure PCTKR2021018681-appb-img-000023
Figure PCTKR2021018681-appb-img-000023
Figure PCTKR2021018681-appb-img-000024
Figure PCTKR2021018681-appb-img-000024
Figure PCTKR2021018681-appb-img-000025
Figure PCTKR2021018681-appb-img-000025
Figure PCTKR2021018681-appb-img-000026
Figure PCTKR2021018681-appb-img-000026
Figure PCTKR2021018681-appb-img-000027
Figure PCTKR2021018681-appb-img-000027
Figure PCTKR2021018681-appb-img-000028
Figure PCTKR2021018681-appb-img-000028
상기 표 1 내지 10의 결과를 보면, 본 발명의 실시예 1 내지 177은 비교예 1 내지 13에 비해, 굴절률, 해상도, 접착력에서 우수함을 나타내고 있으며, 특히 실시예 1 내지 80의 경우 실시예 81 내지 177에 비하여 더욱 우수한 굴절률, 해상도 및 접착력을 나타내고 있다.Looking at the results of Tables 1 to 10, Examples 1 to 177 of the present invention exhibit superiority in refractive index, resolution, and adhesive force compared to Comparative Examples 1 to 13, and in particular, Examples 1 to 80 in Examples 81 to Compared to 177, it shows better refractive index, resolution, and adhesion.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible within the scope without departing from the technical spirit of the present invention described in the claims. It will be apparent to those of ordinary skill in the art.

Claims (18)

  1. 열경화성 작용기를 포함하는 제1 불포화 화합물로부터 유래된 반복단위, 및 불소를 포함하는 제2 불포화 화합물로부터 유래된 반복단위를 포함하는 아크릴계 공중합체;an acrylic copolymer including a repeating unit derived from a first unsaturated compound containing a thermosetting functional group, and a repeating unit derived from a second unsaturated compound containing fluorine;
    광개시제; 및photoinitiators; and
    용매;를 포함하는 네가티브 감광성 수지 조성물.A negative photosensitive resin composition comprising a solvent.
  2. 제1항에 있어서,According to claim 1,
    상기 아크릴계 공중합체는 상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위를 각각 5 내지 30 중량%로 포함하는 네가티브 감광성 수지 조성물. The acrylic copolymer is a negative photosensitive resin composition comprising 5 to 30% by weight of each of the repeating units derived from the first and second unsaturated compounds.
  3. 제1항에 있어서,According to claim 1,
    상기 아크릴계 공중합체는 상기 제1 불포화 화합물로부터 유래된 반복단위를 10 내지 30 중량%, 제2 불포화 화합물로부터 유래된 반복단위를 5 내지 30 중량% 로 포함하는 네가티브 감광성 수지 조성물. The acrylic copolymer is a negative photosensitive resin composition comprising 10 to 30% by weight of the repeating unit derived from the first unsaturated compound and 5 to 30% by weight of the repeating unit derived from the second unsaturated compound.
  4. 제1항에 있어서,According to claim 1,
    상기 아크릴계 공중합체는,The acrylic copolymer,
    상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위를 각각 5 내지 30 중량%; 5 to 30% by weight of each of the repeating units derived from the first and second unsaturated compounds;
    불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물로부터 유래된 반복단위를 1 내지 50 중량%;로 포함하는 것인 네가티브 감광성 수지 조성물.A negative photosensitive resin composition comprising: 1 to 50% by weight of a repeating unit derived from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof.
  5. 제1항에 있어서,According to claim 1,
    상기 아크릴계 공중합체는 상기 제1 및 제2 불포화 화합물로부터 유래된 반복단위를 각각 5 내지 30 중량%, 올레핀 불포화 화합물로부터 유래된 반복단위를 1 내지 50 중량%로 포함하는 네가티브 감광성 수지 조성물.The acrylic copolymer is a negative photosensitive resin composition comprising 5 to 30% by weight of each of the repeating units derived from the first and second unsaturated compounds, and 1 to 50% by weight of the repeating units derived from the olefinically unsaturated compound.
  6. 제1항에 있어서, According to claim 1,
    상기 제1 불포화 화합물은 에폭시기를 갖는 직쇄 또는 측쇄 지방족 구조 또는 에폭시기를 갖는 지환족 구조를 포함하는 네가티브 감광성 수지 조성물.The first unsaturated compound is a negative photosensitive resin composition comprising a linear or branched aliphatic structure having an epoxy group or an alicyclic structure having an epoxy group.
  7. 제1항에 있어서,According to claim 1,
    상기 제1 불포화 화합물은 하기 화학식 1 내지 화학식 3으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함하는 네가티브 감광성 수지 조성물:The first unsaturated compound is a negative photosensitive resin composition comprising at least one structure selected from the group consisting of the following Chemical Formulas 1 to 3:
    [화학식 1][Formula 1]
    Figure PCTKR2021018681-appb-img-000029
    Figure PCTKR2021018681-appb-img-000029
    [화학식 2][Formula 2]
    Figure PCTKR2021018681-appb-img-000030
    Figure PCTKR2021018681-appb-img-000030
    [화학식 3][Formula 3]
    Figure PCTKR2021018681-appb-img-000031
    Figure PCTKR2021018681-appb-img-000031
    상기 화학식 2에서 n은 1 내지 10의 정수이고, 상기 화학식 3에서 R은 탄소수 0 내지 10의 알킬, 알켄, 알릴 구조 중 하나 이상을 가지는 유기기이다.In Formula 2, n is an integer of 1 to 10, and R in Formula 3 is an organic group having at least one of an alkyl, alkene, and allyl structure having 0 to 10 carbon atoms.
  8. 제1항에 있어서,According to claim 1,
    상기 제2 불포화 화합물은 하기 화학식 4 내지 화학식 6으로 이루어진 군으로부터 선택되는 1종 이상의 구조를 포함하는 네가티브 감광성 수지 조성물:The second unsaturated compound is a negative photosensitive resin composition comprising at least one structure selected from the group consisting of the following Chemical Formulas 4 to 6:
    [화학식 4][Formula 4]
    Figure PCTKR2021018681-appb-img-000032
    Figure PCTKR2021018681-appb-img-000032
    [화학식 5][Formula 5]
    Figure PCTKR2021018681-appb-img-000033
    Figure PCTKR2021018681-appb-img-000033
    [화학식 6][Formula 6]
    Figure PCTKR2021018681-appb-img-000034
    Figure PCTKR2021018681-appb-img-000034
    상기 화학식 4에서 n은 0 내지 9의 정수이고, 상기 화학식 5에서 n은 1 내지 10의 정수이며, 상기 화학식 6에서 n은 0 내지 9의 정수이다.In Formula 4, n is an integer of 0 to 9, In Formula 5, n is an integer of 1 to 10, and in Formula 6, n is an integer of 0 to 9.
  9. 제1항에 있어서,According to claim 1,
    상기 아크릴계 공중합체의 중량평균분자량(Mw)은 1,000 내지 10,000인 것인 네가티브 감광성 수지 조성물.The negative photosensitive resin composition of the weight average molecular weight (Mw) of the acrylic copolymer is 1,000 to 10,000.
  10. 제1항에 있어서,According to claim 1,
    상기 광개시제는 상기 아크릴계 공중합체 100 중량부에 대하여, 0.1 내지 30 중량부로 포함된 것인 감광성 수지 조성물.The photoinitiator is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer, the photosensitive resin composition.
  11. 제1항에 있어서,According to claim 1,
    상기 네가티브 감광성 수지 조성물은 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 에틸렌성 불포화 우레탄 올리고머를 더 포함하는 것인 네가티브 감광성 수지 조성물. The negative photosensitive resin composition further comprises an ethylenically unsaturated urethane oligomer in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.
  12. 제11항에 있어서, 12. The method of claim 11,
    상기 에틸렌성 불포화 우레탄 올리고머는 하나 이상의 불소 원자를 포함하는 것인 네가티브 감광성 수지 조성물.The ethylenically unsaturated urethane oligomer is a negative photosensitive resin composition comprising one or more fluorine atoms.
  13. 제1항에 있어서,According to claim 1,
    상기 네가티브 감광성 수지 조성물은 상기 아크릴계 공중합체 100 중량부에 대하여, 1 내지 50 중량부로 에틸렌성 불포화 다관능 모노머를 더 포함하는 것인 네가티브 감광성 수지 조성물.The negative photosensitive resin composition, based on 100 parts by weight of the acrylic copolymer, 1 to 50 parts by weight of the negative photosensitive resin composition further comprising an ethylenically unsaturated polyfunctional monomer.
  14. 제13항에 있어서,14. The method of claim 13,
    상기 에틸렌성 불포화 다관능 모노머는 불소를 포함하고 있는 것인 네가티브 감광성 수지 조성물.The ethylenically unsaturated polyfunctional monomer is a negative photosensitive resin composition containing fluorine.
  15. 제1항에 있어서,According to claim 1,
    상기 용매는 상기 아크릴계 공중합체 100 중량부에 대하여, 10 내지 500 중량부로 포함된 것인 네가티브 감광성 수지 조성물. The solvent is a negative photosensitive resin composition that is included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the acrylic copolymer.
  16. 제1항에 있어서,According to claim 1,
    상기 용매는 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디프로필렌글리콜디메틸에테르, 디포로필렌글리콜디에틸에테르, 부틸렌글리콜모노메틸에테르, 부틸렌글리콜모노에틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에틸에테르, 트리에틸렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르로 이루어지는 군으로부터 선택되는 1종 이상의 용매를 포함하는 것인 네가티브 감광성 수지 조성물.The solvent is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, Propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diphoropylene glycol diethyl ether, butylene glycol monomethyl ether, butyl Renglycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, di group consisting of ethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether and dipropylene glycol methylhexyl ether A negative photosensitive resin composition comprising one or more solvents selected from
  17. 제1항 내지 제16항 중 어느 한 항에 따른 네가티브 감광성 수지 조성물의 경화체를 포함하는 표시장치.A display device comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 16.
  18. 제17항에 있어서, 18. The method of claim 17,
    상기 표시장치는 1.5 이하의 굴절률을 가진 광학부재를 포함하며,The display device includes an optical member having a refractive index of 1.5 or less,
    상기 광학부재는 상기 경화체를 포함하는 것인 표시장치.The optical member is a display device including the curing body.
PCT/KR2021/018681 2020-12-31 2021-12-09 Negative photo-sensitive resin composition with low-temperature curability and low refractive index WO2022145795A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202180086312.7A CN116648671A (en) 2020-12-31 2021-12-09 Negative photosensitive resin composition capable of realizing low-temperature curing and low refractive index

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2020-0189889 2020-12-31
KR1020200189889A KR20220096986A (en) 2020-12-31 2020-12-31 Negative photosensitive resin composition capable of low temperature curing and low refractive index

Publications (1)

Publication Number Publication Date
WO2022145795A1 true WO2022145795A1 (en) 2022-07-07

Family

ID=82260613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2021/018681 WO2022145795A1 (en) 2020-12-31 2021-12-09 Negative photo-sensitive resin composition with low-temperature curability and low refractive index

Country Status (4)

Country Link
KR (1) KR20220096986A (en)
CN (1) CN116648671A (en)
TW (1) TW202235455A (en)
WO (1) WO2022145795A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140003343A (en) * 2012-06-29 2014-01-09 주식회사 엘지화학 Composition for manufacturing resin, resin manufactured by using the same, curable resin composition comprising resin, photosensitive material manufactured by using the photoresist resin composition, and display device comprising the same
JP2016040577A (en) * 2014-08-12 2016-03-24 東京応化工業株式会社 Positive photosensitive resin composition and cured film
KR20180063060A (en) * 2015-09-30 2018-06-11 도레이 카부시키가이샤 DEVICE AND DISPLAY DEVICE COMPRISING A NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, CURED FILM, CURED FILM AND METHOD FOR MANUFACTURING THE SAME
KR20180077743A (en) * 2016-12-29 2018-07-09 주식회사 동진쎄미켐 Negative photosensitive resin composition
KR20190087172A (en) * 2018-01-16 2019-07-24 동우 화인켐 주식회사 Negative-type Photosensitive Resin Composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140003343A (en) * 2012-06-29 2014-01-09 주식회사 엘지화학 Composition for manufacturing resin, resin manufactured by using the same, curable resin composition comprising resin, photosensitive material manufactured by using the photoresist resin composition, and display device comprising the same
JP2016040577A (en) * 2014-08-12 2016-03-24 東京応化工業株式会社 Positive photosensitive resin composition and cured film
KR20180063060A (en) * 2015-09-30 2018-06-11 도레이 카부시키가이샤 DEVICE AND DISPLAY DEVICE COMPRISING A NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, CURED FILM, CURED FILM AND METHOD FOR MANUFACTURING THE SAME
KR20180077743A (en) * 2016-12-29 2018-07-09 주식회사 동진쎄미켐 Negative photosensitive resin composition
KR20190087172A (en) * 2018-01-16 2019-07-24 동우 화인켐 주식회사 Negative-type Photosensitive Resin Composition

Also Published As

Publication number Publication date
TW202235455A (en) 2022-09-16
CN116648671A (en) 2023-08-25
KR20220096986A (en) 2022-07-07

Similar Documents

Publication Publication Date Title
WO2016126070A1 (en) Novel oximester derivative compound, and photopolymerization initiator and photoresist composition containing same
WO2019083112A1 (en) Composition comprising quantum dots, method for preparing quantum dots, and color filter
WO2017057813A1 (en) Binder resin and photosensitive resin composition containing same
WO2015108386A1 (en) Novel β-oximester fluorene compound, a photopolymerization initiator comprising same, and photoresist composition
WO2020050590A1 (en) Compound, colorant composition, photosensitive material, color filter, and display device
WO2019194402A1 (en) Cardo-based binder resin, photosensitive resin composition comprising same, black matrix, color filter, and display device
WO2013100298A1 (en) Positive photosensitive resin composition
WO2021075740A1 (en) Quantum dots, curable composition comprising same, cured film manufactured using composition, and color filter comprising cured film
WO2019107685A1 (en) Method for producing colorant composition, and colorant composition, colorant dispersion, photosensitive resin composition, color filter, liquid crystal display device produced using same
WO2014104496A1 (en) Monomer, hardmask composition including monomer, and method for forming pattern by using hardmask composition
WO2022145795A1 (en) Negative photo-sensitive resin composition with low-temperature curability and low refractive index
WO2021080267A1 (en) Polysiloxane copolymer, method for producing same, and resin composition comprising same
WO2020197179A1 (en) Alkali-soluble, photocurable, and thermosetting copolymer, and photosensitive resin composition, photosensitive resin film, and color filter using same
WO2021075741A1 (en) Quantum dots, curable composition comprising same, cured film manufactured using composition, and color filter comprising cured film
WO2016122160A1 (en) Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same
WO2019164157A1 (en) Compound, colorant composition comprising same, and resin composition comprising same
WO2014193165A1 (en) Photosensitive resin composition for forming spacer, and spacer prepared therefrom
WO2023234561A1 (en) Display device and photo-sensitive resin composition for same
WO2021091222A1 (en) Compound, binder resin, negative-type photosensitive resin composition, and display device comprising black bank formed using same
WO2021091223A1 (en) Binder resin, negative-type photosensitive resin composition, and display device comprising black bank formed using same
WO2021071281A1 (en) Positive photosensitive resin composition and display device using same
WO2019074262A1 (en) Binder resin and photosensitive resin composition or coating solution including same
WO2019022404A1 (en) Polymer for forming bottom anti-reflective coatings and composition for forming bottom anti-reflective coatings comprising same
WO2019194381A1 (en) Quinophthalone-based compound, photosensitive resin composition comprising same, photosensitive material, color filter, and display device
WO2019194384A1 (en) Xanthene-based compound, and photosensitive resin composition, photosensitive material, color filter and display device including same

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: 21915593

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202180086312.7

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21915593

Country of ref document: EP

Kind code of ref document: A1