WO2021010683A1 - Photosensitive resin composition - Google Patents
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- WO2021010683A1 WO2021010683A1 PCT/KR2020/009132 KR2020009132W WO2021010683A1 WO 2021010683 A1 WO2021010683 A1 WO 2021010683A1 KR 2020009132 W KR2020009132 W KR 2020009132W WO 2021010683 A1 WO2021010683 A1 WO 2021010683A1
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- resin composition
- photosensitive resin
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/36—Solid anodes; Solid auxiliary anodes for maintaining a discharge
- H01J1/44—Rotary anodes; Arrangements for rotating anodes; Cooling rotary anodes
Definitions
- the present invention relates to a photosensitive resin composition, and more particularly, since it is suitable for forming a column spacer, a black matrix, or a colored (for example, black) column spacer due to a high residual film rate while implementing a fine pattern, It relates to a photosensitive resin composition that can be used in various electronic components including OLED displays and TFT-LCD panels.
- the photosensitive composition has improved residual film ratio, photosensitive speed, development contrast, resolution, and polymer resin. It must have solubility, adhesion to the substrate, and CD uniformity.
- FIG. 1 An exemplary structure of the column spacer pattern is as shown in FIG. 1.
- the residual film ratio can be improved in the same bottom CD (critical dimension) size, it is possible to reduce the cost of the product by reducing the consumption of the resist material during the manufacturing process.
- Conventional photosensitive resin compositions implement a fine pattern using a photopolymerization initiator having a specific structure or implement a fine pattern through another additive such as a radical scavenger (eg, Korean Patent No. 10-1435652).
- a radical scavenger eg, Korean Patent No. 10-1435652
- the radical functional group generated by exposure from conventional photopolymerization initiators was used to reduce the initiator content in order to make a fine pattern, this has a disadvantage of reducing the residual film rate.
- the present invention is intended to solve the problems of the prior art, and it is an object of the present invention to provide a photosensitive resin composition capable of implementing a fine pattern and increasing a residual film rate.
- the present invention to solve the above technical problem, (a) alkali-soluble binder resin; (b) optionally a photopolymerizable compound; (c) a photopolymerization initiator having a structure represented by the following formula (1); And (d) an organic solvent; and, based on a total of 100 parts by weight of the (a) alkali-soluble binder resin and (b) optionally a photopolymerizable compound, the (c) photopolymerization initiator is 0.7 to 20 parts by weight, including, photosensitive Provides a resin composition:
- R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, a carbon source Embroidery 7-40 arylalkyl groups, 1-20 carbon atoms hydroxyalkyl groups, 2-40 carbon atoms hydroxyalkoxyalkyl groups or 3-20 carbon atoms cycloalkyl group,
- R 3 represents an aryl group having 6-20 carbon atoms.
- the photosensitive resin composition of the present invention may further include a chain transfer agent for controlling molecular weight.
- a fine patterned cured product formed from the photosensitive resin composition of the present invention is provided.
- the photosensitive resin composition of the present invention is suitable for forming a column spacer, a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate.
- a column spacer a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate.
- 1 is an exemplary structure of a column spacer pattern.
- FIG. 2 is a graph showing a film residual rate according to the type of photoinitiator used in Examples and Comparative Examples of the present invention.
- FIG 3 is a graph comparing the absorbance of the photoinitiator C used in the example of the present invention and the photoinitiator OXE-01 used in Comparative Example 7 according to the absorption wavelength.
- the photosensitive resin composition of this invention contains (a) alkali-soluble binder resin.
- the alkali-soluble binder resin may be an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain.
- the acrylic polymer refers to a polymer (including a single polymer or a copolymer) of an acrylic monomer, and examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth) )Acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth) )Acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) Acrylate, di
- an acrylic monomer containing a carboxylic acid such as (meth)acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester; Alkyl (meth) acrylate, such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, ⁇ -methyl Styrene
- acrylic polymer having an acrylic unsaturated bond in the side chain may be a copolymer obtained by adding a carboxylic acid-containing compound to an acrylic copolymer containing an epoxy group.
- An acrylic monomer containing an epoxy group such as an acrylate; Alkyl (meth) acrylate, such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate
- the weight average molecular weight of the alkali-soluble binder resin may be 1,000 or more, 2,000 or more, 3,000 or more, or 4,000 or more, and may be 300,000 or less, 200,000 or less, 100,000 or less, 50,000 or less, or 40,000 or less. , But is not limited thereto.
- the dispersion degree of the alkali-soluble binder resin may be 1.0 or more, 1.2 or more, or 1.5 or more, and may be 10.0 or less, 5.0 or less, or 3.0 or less, but is not limited thereto.
- a binder resin containing an acrylate group, or a novolac or bisphenol type alkali-soluble polymer may be further used.
- additional binder resins that can be used include Nippon Kayaku's PCR-122H, PCR-1173H, PCR-1221H, PCR-1220H, CCR-1171H, CCR-1307H, CCR-1309H, ZAR-1494H, and ZAR-2001H. , ZFR-1491H, ZFR-1554H, and the like, but are not limited thereto.
- the alkali-soluble binder resin may be a random copolymer that is not restricted to the arrangement order of each polymerization unit, but is not limited thereto.
- the content of the alkali-soluble binder resin can be appropriately adjusted as necessary, for example, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight based on the total 100 parts by weight of the composition. Or more, 9 parts by weight or more, or 10 parts by weight or more, and also 99 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, It may be 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, but is not limited thereto.
- the photosensitive resin composition of the present invention may contain a photopolymerizable compound as an optional component (b).
- the photopolymerizable compound may be a crosslinkable monomer having at least two or more ethylenic double bonds.
- the photopolymerizable compound includes, for example, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and propylene oxide groups having 2 to 20 ethylene oxide groups. 14-membered polypropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, addition reaction product of bisphenol A and diglycidyl ether acrylic acid, ethyl isocyanuric acid Tri(meth)acrylate, phthalate diester of ⁇ -hydroxyethyl (meth)acrylate, addition reaction product of ⁇ -hydroxyethyl (meth)acrylate and toluene diisocyanate, trimethylolpropane tri(meth)acrylate , Tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol
- an isocyanurate compound may be used as the photopolymerizable compound.
- isocyanurate compounds that can be used as photopolymerizable compounds include monoallyl diglycidyl isocyanurate compounds, diallyl monoglycidyl isocyanurate compounds, and triallyl isocyanurate compounds.
- examples of the monoallyl diglycidyl isocyanurate compound include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1-(2-methylpropenyl)-3,5-diglycidylisocyanurate, 1-(2-methylpropenyl)-3,5-bis(2-methylepoxypropyl)isocyanurate, etc.
- diallyl monoglycidyl isocyanurate compound examples include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5-(2-methylepoxypropyl)isocyanu Rate, 1,3-bis(2-methylpropenyl)-5-glycidylisocyanurate, 1,3-bis(2-methylpropenyl)-5-(2-methylepoxypropyl)isocyanu Rate and the like
- examples of the triallyl isocyanurate compound include triallyl isocyanurate, tris(2-methylpropenyl)isocyanurate, and the like, and any one or two selected from among them The above may be mixed and used, but the present invention is not limited thereto.
- the content when the photopolymerizable compound is included, the content can be appropriately adjusted as necessary, for example, 2 parts by weight or more, 4 parts by weight or more, based on the total 100 parts by weight of the composition, It may be 6 parts by weight or more, 8 parts by weight or more, or 10 parts by weight or more, and may be 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less, but is not limited thereto. .
- the photosensitive resin composition of the present invention includes (c) a photopolymerization initiator having a structure represented by the following formula (1).
- R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, and 1-20 carbon atoms 4 alkoxy groups, 7-40 carbon atoms arylalkyl groups, 1-20 carbon atoms hydroxyalkyl groups, 2-40 carbon atoms hydroxyalkoxyalkyl groups, or 3-20 carbon atoms cycloalkyl groups; R 3 represents an aryl group having 6-20 carbon atoms.
- R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-16 carbon atoms, an aryl group having 6-14 carbon atoms, and a carbon source Embroidery 1-16 alkoxy groups, 7-30 carbon atoms arylalkyl groups, 1-16 carbon atoms hydroxyalkyl groups, 2-32 carbon atoms hydroxyalkoxyalkyl groups or 3-16 carbon atoms cycloalkyl groups, R 3 represents an aryl group having 6-14 carbon atoms.
- R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, Represents an alkoxy group having 1-10 carbon atoms, an arylalkyl group having 7-20 carbon atoms, a hydroxyalkyl group having 1-10 carbon atoms, a hydroxyalkoxyalkyl group having 2-20 carbon atoms, or a cycloalkyl group having 3-10 carbon atoms, R 3 represents an aryl group having 6-10 carbon atoms.
- R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-6 carbon atoms, an aryl group having 6-10 carbon atoms, Represents an alkoxy group having 1-6 carbon atoms, an arylalkyl group having 7-16 carbon atoms, a hydroxyalkyl group having 1-6 carbon atoms, a hydroxyalkoxyalkyl group having 2-12 carbon atoms, or a cycloalkyl group having 3-6 carbon atoms, R 3 represents an aryl group having 6-10 carbon atoms.
- the linear or branched alkyl group, aryl group, alkoxy group, arylalkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, and cycloalkyl group are each independently unsubstituted, or halogen, linear having 1-6 carbon atoms Or it may be substituted by a branched alkyl group or a cycloalkyl group having 3-6 carbon atoms.
- R 1 is each independently hydrogen, methyl group, ethyl group, propyl group, or butyl group;
- R 2 is a methyl group, an ethyl group, a propyl group or a butyl group;
- R 3 is a phenyl group;
- R 4 to R 10 may be hydrogen.
- the photopolymerization initiator having the structure represented by Formula 1 imparts excellent film retention properties to the photosensitive resin composition of the present invention, and in particular, compared to the conventional photopolymerization initiator having an alkyl group (eg, methyl group, ethyl group, etc.) at the R 3 position. , And provides excellent residual film rate characteristics at the same fine pattern size.
- an alkyl group eg, methyl group, ethyl group, etc.
- the (c) photopolymerization initiator of Formula 1 is in an amount of 0.7 to 20 parts by weight. Included as. Low sensitivity if the amount of the photopolymerization initiator of Formula 1 contained in the photosensitive resin composition of the present invention is less than 0.7 parts by weight based on 100 parts by weight of the total of (a) an alkali-soluble binder resin and (b) an optional photopolymerizable compound. Due to this, the residual film rate may be deteriorated and there may be difficulties in pattern formation. If it exceeds 20 parts by weight, a problem may occur in storage stability, and foreign matter may be generated on the surface of the thin film due to a decrease in solubility of the photopolymerization initiator.
- the amount of the photopolymerization initiator of Formula 1 included in the photosensitive resin composition of the present invention is 0.8 parts by weight or more, 0.9 parts by weight based on 100 parts by weight of the total of (a) alkali-soluble binder resin and (b) photopolymerizable compound.
- It may be at least 1.0 part by weight, at least 1.1 parts by weight, at least 1.2 parts by weight, at least 1.4 parts by weight, at least 1.6 parts by weight, or at least 1.8 parts by weight, and also 19.5 parts by weight or less, 19 parts by weight or less, 18.5 parts by weight It may be 18 parts by weight or less, 16 parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, or 8 parts by weight or less.
- the photosensitive resin composition of the present invention may further include, if necessary, an additional photopolymerization initiator in addition to the photopolymerization initiator of Formula 1 above.
- Photoinitiator compounds that can be additionally used in the present invention include commonly used photoinitiator compounds such as triazine-based, benzoin-based, acetophenone-based, imidazole-based, xanthone-based or oxime ester-based, and more specifically, triazine Phenylphosphine oxide, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzyldimethylketal, 1-benzyl-1-dimethylamino-1-(4-morpholino-benzoyl)propane, 2-mo Polyl-2-(4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propyl thioxanthone, isopropyl thi
- the photosensitive resin composition of this invention contains (d) an organic solvent.
- organic solvent examples include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate
- N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetate Amide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. Solvents selected from the above can be used alone or in combination of two or more.
- the content of the organic solvent can be appropriately adjusted as necessary, for example, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight based on the total 100 parts by weight of the composition. It may be greater than or equal to 50 parts by weight, and may be 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less, but is not limited thereto. There is no particular limitation on the solid content concentration of the photosensitive resin composition of the present invention, and in one embodiment, the solid content concentration may be 10 to 50% by weight, but is not limited thereto.
- the photosensitive resin composition of the present invention may further include a chain transfer agent for controlling molecular weight.
- a sulfur atom-containing compound may be used as a chain transfer agent for molecular weight control.
- the sulfur atom-containing chain transfer agent for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl) Glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropi) O'Nyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercaptobuta
- the content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 5 parts by weight, more specifically 0.5 to 2 parts by weight, but is not limited thereto.
- the photosensitive resin composition of the present invention optionally includes a filler, other polymer compounds, thermal radical generators, ultraviolet absorbers, adhesion promoters, polymerization regulators, pH regulators, scale inhibitors, electrolytes, etc. It may further contain additives known in the art. The types and contents of these additional additives are not particularly limited and may be used in conventional types and contents known in the art.
- the photosensitive composition of the present invention may further include one or more additional components, such as a colorant, a co-curing agent, an adhesion aid, and/or a surfactant, if necessary.
- additional components such as a colorant, a co-curing agent, an adhesion aid, and/or a surfactant, if necessary.
- the colorant may include an organic pigment, a dye, or a combination thereof.
- the organic pigment may be one or a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment.
- a black inorganic colorant, a black organic colorant, or a mixture thereof may be included.
- the red pigment is C.I. in the Color Index. Red pigment 179, C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89, etc. may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
- the green pigment is C.I. in the Color Index. Green pigment 59, C.I. Green pigment 58, C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
- the blue pigment is C.I. in the Color Index. Blue pigment 15:6, C.I. Blue pigment 15:0, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I blue pigment 15:6, C.I. Blue pigment 16 may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
- the yellow pigment is C.I. in the Color Index. Isoindolin-based pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. Nickel complex pigments such as yellow pigment 150, C.I. Yellow pigment 100 or the like may be used, and these may be used alone or in combination of two or more, but the present invention is not limited thereto.
- black inorganic colorant carbon black, titanium black, Cu-Fe-Mn-based oxide, and metal oxide such as synthetic iron black may be used, and these may be used alone or in combination of two or more, It is not necessarily limited thereto.
- black organic colorant examples include aniline black, lactam black, and perylene black, among which lactam black (eg, BASF's Black 582, etc.) may be used, and these may be used alone or in combination of two or more. It can be used, but is not necessarily limited thereto.
- a pigment When a pigment is used as the colorant, it may be added to the colored photosensitive resin composition in the form of a colored dispersion (mill base) mixed with a dispersant, a copolymer resin, a solvent, etc. to disperse the pigment.
- the content may be appropriately adjusted as necessary, for example, in an amount of 1 to 40 parts by weight, more specifically 2 to 20 parts by weight based on the total 100 parts by weight of the composition. Parts by weight, and more specifically, may be included in an amount of 5 to 10 parts by weight, but is not limited thereto.
- the auxiliary curing agent acts to generate radicals of the photoinitiator and enhance the degree of curing of the thin film, examples of which include pentaerythritol tetrakis (3-mercaptopropionate), dioctylphthalate, diisononylphthalate, dioctyl adipate, Tricresylphosphate, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2, 5,-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, and the like, and these may be used alone or in combination of two or more, but must be limited thereto It does not become.
- pentaerythritol tetrakis (3-mercaptopropionate) dioctylphthalate, dii
- auxiliary curing agent When the auxiliary curing agent is included in the photosensitive resin composition of the present invention, its content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 8 parts by weight, more specifically 0.4 to 5 parts by weight, but is not limited thereto.
- the adhesion aid may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate and the like.
- a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate and the like.
- the adhesion aids include trimethoxysilyl benzoic acid, ⁇ -methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, ⁇ -isocyanate propyl triethoxysilane, ⁇ -gly Cidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.
- the adhesive auxiliary agent is included in the photosensitive resin composition of the present invention, the content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 8 parts by weight, more specifically 0.4 to 5 parts by weight, but is not limited thereto.
- the surfactant serves to improve the coatability or developability of the photosensitive resin composition, and the type is not particularly limited, and may be, for example, a fluorine-based surfactant or a silicone surfactant.
- fluorine-based surfactants include BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M), SH-28PA/-190/SZ-6032 (Tore Silicon Co., Ltd.).
- Commercially available products of the silicone surfactant include BYK's BYK-310, BYK-313, BYK-320, BYK-333, and the like, but are not limited thereto.
- the content can be appropriately adjusted as needed, for example, in an amount of 0.01 to 5 parts by weight, more specifically 0.02 to It may be included in an amount of 4 parts by weight, more specifically 0.05 to 2 parts by weight, but is not limited thereto.
- the photosensitive resin composition of the present invention is suitable for forming a column spacer, a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate.
- a column spacer a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate.
- a fine patterned cured product formed from the photosensitive resin composition of the present invention is provided.
- the finely patterned cured product may be a column spacer, a black matrix, or a colored (eg, black) column spacer.
- the fine patterned cured product may be formed by, for example, applying the photosensitive resin composition of the present invention onto a substrate, followed by patterning exposure and development, but is not limited thereto.
- a binder resin 13 parts by weight
- a polymerizable compound having an unsaturated bond 26 parts by weight
- a photopolymerization initiator 60 parts by weight
- a solvent 60 parts by weight
- Binder resin acrylic polymer obtained in Preparation Example
- the size of the prepared pattern was measured using SNU's SNU equipment.
- the film thickness before exposure and the rate of change in the thickness of the final cured film were calculated as the residual film rate.
- Remaining film rate (%) [Thickness after curing / thickness before exposure] * 100
- photoinitiator C has a higher residual film rate than OXE-01 (Comparative Example 7), which is widely used in the past while generating the same radicals, which is shown in FIG. This is believed to be because the area that absorbs light of OXE-01 is larger than that of OXE-01.
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Abstract
The present invention relates to a photosensitive resin composition, and more specifically, to a photosensitive resin composition which is capable of realizing micropatterns, and due to high retention rate, is also suitable for forming a column spacer, a black matrix, or a color (for example, black) column spacer, and thus may be used in various electronic parts including an OLED display and a TFT-LCD panel.
Description
본 발명은 감광성 수지 조성물에 관한 것으로서, 보다 상세하게는, 미세 패턴을 구현함과 동시에 잔막율이 높아 컬럼 스페이서, 블랙 매트릭스, 또는 착색(예컨대, 블랙) 컬럼 스페이서를 형성하는 데에 적합하기 때문에, OLED 디스플레이 및 TFT-LCD 패널을 비롯한 다양한 전자 부품에 사용될 수 있는 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition, and more particularly, since it is suitable for forming a column spacer, a black matrix, or a colored (for example, black) column spacer due to a high residual film rate while implementing a fine pattern, It relates to a photosensitive resin composition that can be used in various electronic components including OLED displays and TFT-LCD panels.
최근 디스플레이 산업은 크게 TV용 디스플레이, 노트북 및 컴퓨터 모니터용의 중소형 디스플레이와, 10인치 이하의 모바일 디스플레이 시장으로 크게 나누어지고 있다. 디스플레이 시장은 해마다 고해상도의 제품을 요구함에 따라 TFT-LCD의 집적도가 향상되어야 하는 과제를 안고 있으며, LCD의 가격 하락으로 인해 생산 원가를 낮추어야 할 필요도 있다. Recently, the display industry is largely divided into TV displays, small and medium-sized displays for notebooks and computer monitors, and mobile displays of 10 inches or less. As the display market demands high-resolution products every year, the integration of TFT-LCDs needs to be improved, and there is a need to lower production costs due to falling LCD prices.
액정 표시 소자에 들어가는 블랙 매트릭스, 컬럼 스페이서 등은 상판과 하판의 갭을 유지하는 역할을 하며, 이러한 미세 패턴을 형성하기 위해서는, 감광성 조성물이 향상된 잔막율, 감광 속도, 현상 콘트라스트, 해상도, 고분자 수지의 용해성, 기판과의 접착력 및 회로 선폭 균일도(CD uniformity)를 가져야 한다.The black matrix, column spacer, etc. that enter the liquid crystal display device play a role in maintaining the gap between the upper plate and the lower plate, and in order to form such a fine pattern, the photosensitive composition has improved residual film ratio, photosensitive speed, development contrast, resolution, and polymer resin. It must have solubility, adhesion to the substrate, and CD uniformity.
컬럼 스페이서 패턴의 예시적인 구조는 도 1에 나타낸 바와 같다. 이러한 컬럼 스페이서 패턴에서, 동일한 Bottom CD(critical dimension) size에서 잔막율을 향상시킬 수 있다면 제조 공정 시 레지스트 재료의 소비를 줄여 제품 가격을 낮출 수 있다.An exemplary structure of the column spacer pattern is as shown in FIG. 1. In such a column spacer pattern, if the residual film ratio can be improved in the same bottom CD (critical dimension) size, it is possible to reduce the cost of the product by reducing the consumption of the resist material during the manufacturing process.
종래의 감광성 수지 조성물들은 특정 구조의 광중합 개시제를 사용하여 미세 패턴을 구현하거나 라디칼 스캐빈저와 같은 다른 첨가물을 통해 미세 패턴을 구현하였다(예: 대한민국등록특허 제10-1435652호). 그러나, 종래의 광중합 개시제들로부터 노광에 의해 발생된 라디칼 작용기는 미세패턴을 만들기 위해서 개시제 함량을 줄이는 방법을 사용하였지만 이는 잔막율을 감소시키는 단점을 가지고 있다.Conventional photosensitive resin compositions implement a fine pattern using a photopolymerization initiator having a specific structure or implement a fine pattern through another additive such as a radical scavenger (eg, Korean Patent No. 10-1435652). However, although the radical functional group generated by exposure from conventional photopolymerization initiators was used to reduce the initiator content in order to make a fine pattern, this has a disadvantage of reducing the residual film rate.
본 발명은 상기한 종래 기술의 문제점을 해결하고자 한 것으로, 미세 패턴을 구현할 수 있는 동시에 잔막율을 높일 수 있는 감광성 수지 조성물을 제공하는 것을 기술적 과제로 한다.The present invention is intended to solve the problems of the prior art, and it is an object of the present invention to provide a photosensitive resin composition capable of implementing a fine pattern and increasing a residual film rate.
상기한 기술적 과제를 해결하고자 본 발명은, (a) 알칼리 가용성 바인더 수지; (b) 임의로 광중합성 화합물; (c) 하기 화학식 1로 표시되는 구조를 갖는 광중합 개시제; 및 (d) 유기 용매;를 포함하며, 상기 (a) 알칼리 가용성 바인더 수지와 (b) 임의로 광중합성 화합물의 합계 100 중량부를 기준으로, 상기 (c) 광중합 개시제 0.7 내지 20 중량부를 포함하는, 감광성 수지 조성물을 제공한다:The present invention to solve the above technical problem, (a) alkali-soluble binder resin; (b) optionally a photopolymerizable compound; (c) a photopolymerization initiator having a structure represented by the following formula (1); And (d) an organic solvent; and, based on a total of 100 parts by weight of the (a) alkali-soluble binder resin and (b) optionally a photopolymerizable compound, the (c) photopolymerization initiator is 0.7 to 20 parts by weight, including, photosensitive Provides a resin composition:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-20개의 선형 또는 분지형 알킬기, 탄소원자수 6-20개의 아릴기, 탄소원자수 1-20 개의 알콕시기, 탄소원자수 7-40 개의 아릴알킬기, 탄소원자수 1-20 개의 히드록시알킬기, 탄소원자수 2-40 개의 히드록시알콕시알킬기 또는 탄소원자수 3-20 개의 사이클로알킬기를 나타내고,R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, a carbon source Embroidery 7-40 arylalkyl groups, 1-20 carbon atoms hydroxyalkyl groups, 2-40 carbon atoms hydroxyalkoxyalkyl groups or 3-20 carbon atoms cycloalkyl group,
R3은 탄소원자수 6-20개의 아릴기를 나타낸다.R 3 represents an aryl group having 6-20 carbon atoms.
일 구체예에서, 본 발명의 감광성 수지 조성물은 분자량 조절을 위한 연쇄이동제를 추가로 포함할 수 있다.In one embodiment, the photosensitive resin composition of the present invention may further include a chain transfer agent for controlling molecular weight.
본 발명의 다른 측면에 따르면, 본 발명의 감광성 수지 조성물로부터 형성되는 미세 패턴화 경화물이 제공된다.According to another aspect of the present invention, a fine patterned cured product formed from the photosensitive resin composition of the present invention is provided.
본 발명의 감광성 수지 조성물은 미세 패턴을 구현할 수 있는 동시에, 잔막율을 높일 수 있어, 컬럼 스페이서, 블랙 매트릭스, 또는 착색(예컨대, 블랙) 컬럼 스페이서를 형성하는 데에 적합하기 때문에, OLED 디스플레이 및 TFT-LCD 패널을 비롯한 다양한 전자 부품에 사용될 수 있다.The photosensitive resin composition of the present invention is suitable for forming a column spacer, a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate. -Can be used for various electronic parts including LCD panels.
도 1은 컬럼 스페이서 패턴의 예시적인 구조이다.1 is an exemplary structure of a column spacer pattern.
도 2는 본 발명의 실시예 및 비교예에서 사용된 광개시제의 종류에 따른 잔막율을 도시한 그래프이다.2 is a graph showing a film residual rate according to the type of photoinitiator used in Examples and Comparative Examples of the present invention.
도 3은 본 발명의 실시예에서 사용된 광개시제 C와 비교예 7에서 사용된 광개시제 OXE-01의 흡수광 파장에 따른 흡광도를 비교한 그래프이다.3 is a graph comparing the absorbance of the photoinitiator C used in the example of the present invention and the photoinitiator OXE-01 used in Comparative Example 7 according to the absorption wavelength.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 감광성 수지 조성물은 (a) 알칼리 가용성 바인더 수지를 포함한다.The photosensitive resin composition of this invention contains (a) alkali-soluble binder resin.
일 구체예에서, 상기 알칼리 가용성 바인더 수지로는 아크릴 중합체 또는 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체를 사용할 수 있다. In one embodiment, the alkali-soluble binder resin may be an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain.
상기 아크릴 중합체는 아크릴계 단량체의 중합체(단독 중합체 또는 공중합체를 포함)를 의미하고, 이러한 단량체의 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타)아크릴레이트, 테트라데실(메타)아크릴레이트, 헥사데실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디사이클로펜타닐(메타)아크릴레이트, 디사이클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, (메타)아크릴산, 이타코닉산, 말레익산, 말레익산 무수물, 말레익산모노알킬 에스테르, 모노알킬 이타코네이트, 모노알킬 퓨말레이트, 글리시딜 (메타)아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시사이클로헥실(메타)아크릴레이트, 3,4-에폭시사이클로헥실메틸(메타)아크릴레이트, 3-메틸옥세탄-3-메틸(메타)아크릴레이트, 3-에틸옥세탄-3-메틸(메타)아크릴레이트, 스티렌, α-메틸스티렌, 아세톡시스티렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-사이클로헥실말레이미드, (메타)아크릴아미드 또는 N-메틸(메타)아크릴아미드 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 함께 사용할 수 있다.The acrylic polymer refers to a polymer (including a single polymer or a copolymer) of an acrylic monomer, and examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth) )Acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth) )Acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) Acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate , (Meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumalate, glycidyl (meth)acrylate, 3,4-epoxybutyl ( Meth)acrylate, 2,3-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-methyloxetane-3-methyl(meth)acrylate, 3-ethyl Oxetane-3-methyl (meth)acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclo Hexylmaleimide, (meth)acrylamide, or N-methyl(meth)acrylamide, and the like, and these may be used alone or in combination of two or more.
또한, 상기 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체로는 카르복실산을 함유한 아크릴 중합체에 에폭시 수지를 부가 반응한 공중합체를 사용할 수 있다. 일 구체예에 따르면, (메타)아크릴산, 이타코닉산, 말레익산 또는 말레익산모노알킬 에스테르 등의 카르복실산을 함유한 아크릴 모노머와; 메틸(메타)아크릴레이트 또는 헥실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디사이클로펜타닐(메타)아크릴레이트, 디사이클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 스티렌, α-메틸스티렌, 아세톡시스티렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-사이클로헥실말레이미드, (메타)아크릴아미드 또는 N-메틸(메타)아크릴아미드 등의 모노머 2종 이상을 공중합하여 얻은 카르복실산을 함유한 아크릴 공중합체에 글리시딜(메타)아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시사이클로헥실(메타)아크릴레이트 또는 3,4-에폭시사이클로헥실메틸(메타)아크릴레이트 등의 에폭시 화합물을, 예컨대 40 내지 180℃의 온도에서 부가 반응하여 얻어진 바인더 수지를 사용할 수 있다.Further, as the acrylic polymer having an acrylic unsaturated bond in the side chain, a copolymer obtained by adding an epoxy resin to an acrylic polymer containing a carboxylic acid may be used. According to an embodiment, an acrylic monomer containing a carboxylic acid such as (meth)acrylic acid, itaconic acid, maleic acid or maleic acid monoalkyl ester; Alkyl (meth) acrylate, such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methyl Styrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide or N-methyl(meth)acrylic Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 2,3-epoxycyclohexyl in an acrylic copolymer containing carboxylic acid obtained by copolymerizing two or more monomers such as amide ( A binder resin obtained by addition reaction of an epoxy compound such as meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate at a temperature of, for example, 40 to 180°C can be used.
측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체의 또 다른 예로는 에폭시기를 함유한 아크릴 공중합체에 카르복실산-함유 화합물을 부가 반응한 공중합체를들 수 있다. 일 구체예에 따르면, 글리시딜(메타)아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시사이클로헥실(메타)아크릴레이트 또는 3,4-에폭시사이클로헥실메틸(메타)아크릴레이트 등의 에폭시기를 함유한 아크릴 모노머와; 메틸(메타)아크릴레이트 또는 헥실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디사이클로펜타닐(메타)아크릴레이트, 디사이클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 스티렌, α-메틸스티렌, 아세톡시스티렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴아미드 또는 N-메틸(메타)아크릴아미드 등의 모노머 2종 이상을 공중합하여 얻은 에폭시기를 함유한 아크릴 공중합체에 (메타)아크릴산 이타코닉산, 말레익산 또는 말레익산모노알킬 에스테르 등의 카르복실산을 함유한 아크릴 모노머를, 예컨대 40 내지 180℃의 온도에서 부가 반응하여 얻어진 바인더 수지를 사용할 수 있다.Another example of the acrylic polymer having an acrylic unsaturated bond in the side chain may be a copolymer obtained by adding a carboxylic acid-containing compound to an acrylic copolymer containing an epoxy group. According to one embodiment, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) ) An acrylic monomer containing an epoxy group such as an acrylate; Alkyl (meth) acrylate, such as methyl (meth) acrylate or hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methyl Styrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide or N-methyl(meth)acrylic An acrylic monomer containing a carboxylic acid such as (meth)acrylic acid itaconic acid, maleic acid or maleic acid monoalkyl ester in an acrylic copolymer containing an epoxy group obtained by copolymerizing two or more monomers such as amide, for example, 40 to A binder resin obtained by addition reaction at a temperature of 180°C can be used.
본 발명의 일 구체예에 따르면, 상기 알칼리 가용성 바인더 수지의 중량평균분자량은 1,000 이상, 2,000 이상, 3,000 이상 또는 4,000 이상일 수 있고, 또한 300,000 이하, 200,000 이하, 100,000 이하, 50,000 이하 또는 40,000 이하일 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment of the present invention, the weight average molecular weight of the alkali-soluble binder resin may be 1,000 or more, 2,000 or more, 3,000 or more, or 4,000 or more, and may be 300,000 or less, 200,000 or less, 100,000 or less, 50,000 or less, or 40,000 or less. , But is not limited thereto.
본 발명의 일 구체예에 따르면, 상기 알칼리 가용성 바인더 수지의 분산도는 1.0 이상, 1.2 이상 또는 1.5 이상일 수 있고, 또한 10.0 이하, 5.0 이하 또는 3.0 이하일 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment of the present invention, the dispersion degree of the alkali-soluble binder resin may be 1.0 or more, 1.2 or more, or 1.5 or more, and may be 10.0 or less, 5.0 or less, or 3.0 or less, but is not limited thereto.
본 발명의 일 구체예에 따르면, 상기 알칼리 가용성 바인더 수지 이외에도, 아크릴레이트 기를 함유한 바인더 수지, 또는 노볼락 또는 비스페놀 타입의 알칼리 가용성 중합체의 추가 사용이 가능하다. 판매되고 있는 제품 중에서 추가 사용 가능한 바인더 수지로는 Nippon Kayaku사의 PCR-122H, PCR-1173H, PCR-1221H, PCR-1220H, CCR-1171H, CCR-1307H, CCR-1309H, ZAR-1494H, ZAR-2001H, ZFR-1491H, ZFR-1554H 등이 있으나, 이에 한정되는 것은 아니다. According to one embodiment of the present invention, in addition to the alkali-soluble binder resin, a binder resin containing an acrylate group, or a novolac or bisphenol type alkali-soluble polymer may be further used. Among the products on sale, additional binder resins that can be used include Nippon Kayaku's PCR-122H, PCR-1173H, PCR-1221H, PCR-1220H, CCR-1171H, CCR-1307H, CCR-1309H, ZAR-1494H, and ZAR-2001H. , ZFR-1491H, ZFR-1554H, and the like, but are not limited thereto.
상기 알칼리 가용성 바인더 수지는 각 중합 단위의 배열 순서에 구속되지 않는 랜덤 공중합체일 수 있으나, 이에 한정되는 것은 아니다.The alkali-soluble binder resin may be a random copolymer that is not restricted to the arrangement order of each polymerization unit, but is not limited thereto.
본 발명의 감광성 수지 조성물에 있어서, 상기 알칼리 가용성 바인더 수지의 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면, 조성물 총 100 중량부에 대하여 3 중량부 이상, 5 중량부 이상, 7 중량부 이상, 9 중량부 이상 또는 10 중량부 이상일 수 있고, 또한 99중량부 이하, 90 중량부 이하, 80 중량부 이하, 70 중량부 이하, 60 중량부 이하, 50 중량부 이하, 45 중량부 이하, 40 중량부 이하, 35 중량부 이하 또는 30 중량부 이하일 수 있으나, 이에 한정되는 것은 아니다.In the photosensitive resin composition of the present invention, the content of the alkali-soluble binder resin can be appropriately adjusted as necessary, for example, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight based on the total 100 parts by weight of the composition. Or more, 9 parts by weight or more, or 10 parts by weight or more, and also 99 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, It may be 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, but is not limited thereto.
본 발명의 감광성 수지 조성물은 (b) 임의 성분으로서 광중합성 화합물을 포함할 수 있다.The photosensitive resin composition of the present invention may contain a photopolymerizable compound as an optional component (b).
상기 광중합성 화합물은 적어도 2 개 이상의 에틸렌계 이중 결합을 가지는 가교성 모노머일 수 있다.The photopolymerizable compound may be a crosslinkable monomer having at least two or more ethylenic double bonds.
일 구체예에서, 상기 광중합성 화합물로는, 예를 들면, 에틸렌옥사이드기의 수가 2 내지 20인 폴리에틸렌글리콜디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 폴리프로필렌글리콜디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 트리메틸올프로판디(메트)아크릴레이트, 비스페놀 A와 디글리시딜에테르아크릴산의 부가반응 생성물, 에틸이소시아눌릭산트리(메트)아크릴레이트, β-히드록시에틸(메트)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메트)아크릴레이트와 톨루엔 디이소시아네이트의 부가반응 생성물, 트리메틸올프로판트리(메트)아크릴레이트, 테트라메틸올메탄테트라(메트)아크릴레이트, 펜타에리스리톨트리(메트)아크릴레이트, 펜타에리스리톨테트라(메트)아크릴레이트, 디펜타에리스리톨펜타(메트)아크릴레이트, 디펜타에리스리톨헥사(메트)아크릴레이트, 디펜타에리스리톨트리(메트)아크릴레이트, 트리메틸올과 프로판트리글리시딜에테르아크릴산의 부가반응 생성물, 노볼락에폭시수지와 (메트)아크릴산의 부가반응 생성물에 프탈산무수물을 반응하여 생성된 노볼락 에폭시 아크릴레이트 수지, 또는 이들의 조합을 사용할 수 있으나, 이에 한정되지는 않는다.In one embodiment, the photopolymerizable compound includes, for example, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and propylene oxide groups having 2 to 20 ethylene oxide groups. 14-membered polypropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, addition reaction product of bisphenol A and diglycidyl ether acrylic acid, ethyl isocyanuric acid Tri(meth)acrylate, phthalate diester of β-hydroxyethyl (meth)acrylate, addition reaction product of β-hydroxyethyl (meth)acrylate and toluene diisocyanate, trimethylolpropane tri(meth)acrylate , Tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Dipentaerythritol tri(meth)acrylate, the addition reaction product of trimethylol and propanetriglycidyl ether acrylic acid, the novolac epoxy acrylate produced by reacting phthalic anhydride with the addition reaction product of novolac epoxy resin and (meth)acrylic acid Resin, or a combination thereof may be used, but is not limited thereto.
다른 구체예에서, 상기 광중합성 화합물로는 이소시아누레이트 화합물을 사용할 수 있다. 광중합성 화합물로 사용 가능한 이소시아누레이트 화합물로는 모노알릴디글리시딜이소시아누레이트 화합물, 디알릴모노글리시딜이소시아누레이트 화합물, 트리알릴이소시아누레이트 화합물 등을 들 수 있다. In another embodiment, an isocyanurate compound may be used as the photopolymerizable compound. Examples of isocyanurate compounds that can be used as photopolymerizable compounds include monoallyl diglycidyl isocyanurate compounds, diallyl monoglycidyl isocyanurate compounds, and triallyl isocyanurate compounds.
구체적으로, 상기 모노알릴디글리시딜이소시아누레이트 화합물의 예로는 모노알릴디글리시딜이소시아누레이트, 1-알릴-3,5-비스(2-메틸에폭시프로필)이소시아누레이트, 1-(2-메틸프로페닐)-3,5-디글리시딜이소시아누레이트, 1-(2-메틸프로페닐)-3,5-비스(2-메틸에폭시프로필)이소시아누레이트 등을 들 수 있고, 상기 디알릴모노글리시딜이소시아누레이트 화합물의 예로는 디알릴모노글리시딜이소시아누레이트, 1,3-디알릴-5-(2-메틸에폭시프로필)이소시아누레이트, 1,3-비스(2-메틸프로페닐)-5-글리시딜이소시아누레이트, 1,3-비스(2-메틸프로페닐)-5-(2-메틸에폭시프로필)이소시아누레이트 등을 들 수 있으며, 상기 트리알릴이소시아누레이트 화합물의 예로는 트리알릴이소시아누레이트, 트리스(2-메틸프로페닐)이소시아누레이트 등을 들 수 있고, 이 중에서 선택된 어느 하나 또는 둘 이상을 혼합하여 사용할 수 있으나, 이에 한정되지는 않는다.Specifically, examples of the monoallyl diglycidyl isocyanurate compound include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1-(2-methylpropenyl)-3,5-diglycidylisocyanurate, 1-(2-methylpropenyl)-3,5-bis(2-methylepoxypropyl)isocyanurate, etc. Examples of the diallyl monoglycidyl isocyanurate compound include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5-(2-methylepoxypropyl)isocyanu Rate, 1,3-bis(2-methylpropenyl)-5-glycidylisocyanurate, 1,3-bis(2-methylpropenyl)-5-(2-methylepoxypropyl)isocyanu Rate and the like, and examples of the triallyl isocyanurate compound include triallyl isocyanurate, tris(2-methylpropenyl)isocyanurate, and the like, and any one or two selected from among them The above may be mixed and used, but the present invention is not limited thereto.
본 발명의 감광성 수지 조성물에 있어서, 상기 광중합성 화합물이 포함되는 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 2 중량부 이상, 4 중량부 이상, 6 중량부 이상, 8 중량부 이상 또는 10 중량부 이상일 수 있고, 또한 70 중량부 이하, 65 중량부 이하, 60 중량부 이하, 55 중량부 이하 또는 50 중량부 이하일 수 있으나, 이에 한정되는 것은 아니다.In the photosensitive resin composition of the present invention, when the photopolymerizable compound is included, the content can be appropriately adjusted as necessary, for example, 2 parts by weight or more, 4 parts by weight or more, based on the total 100 parts by weight of the composition, It may be 6 parts by weight or more, 8 parts by weight or more, or 10 parts by weight or more, and may be 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less, but is not limited thereto. .
본 발명의 감광성 수지 조성물은 (c) 하기 화학식 1로 표시되는 구조를 갖는 광중합 개시제를 포함한다.The photosensitive resin composition of the present invention includes (c) a photopolymerization initiator having a structure represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-20개의 선형 또는 분지형 알킬기, 탄소원자수 6-20개의 아릴기, 탄소원자수 1-20 개의 알콕시기, 탄소원자수 7-40 개의 아릴알킬기, 탄소원자수 1-20 개의 히드록시알킬기, 탄소원자수 2-40 개의 히드록시알콕시알킬기 또는 탄소원자수 3-20 개의 사이클로알킬기를 나타내고; R3은 탄소원자수 6-20개의 아릴기를 나타낸다.In Formula 1, R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, and 1-20 carbon atoms 4 alkoxy groups, 7-40 carbon atoms arylalkyl groups, 1-20 carbon atoms hydroxyalkyl groups, 2-40 carbon atoms hydroxyalkoxyalkyl groups, or 3-20 carbon atoms cycloalkyl groups; R 3 represents an aryl group having 6-20 carbon atoms.
보다 구체적으로, 상기 화학식 1에서, R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-16개의 선형 또는 분지형 알킬기, 탄소원자수 6-14개의 아릴기, 탄소원자수 1-16 개의 알콕시기, 탄소원자수 7-30 개의 아릴알킬기, 탄소원자수 1-16 개의 히드록시알킬기, 탄소원자수 2-32 개의 히드록시알콕시알킬기 또는 탄소원자수 3-16 개의 사이클로알킬기를 나타내고, R3은 탄소원자수 6-14개의 아릴기를 나타낸다.More specifically, in Formula 1, R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-16 carbon atoms, an aryl group having 6-14 carbon atoms, and a carbon source Embroidery 1-16 alkoxy groups, 7-30 carbon atoms arylalkyl groups, 1-16 carbon atoms hydroxyalkyl groups, 2-32 carbon atoms hydroxyalkoxyalkyl groups or 3-16 carbon atoms cycloalkyl groups, R 3 represents an aryl group having 6-14 carbon atoms.
보다 더 구체적으로, 상기 화학식 1에서, R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-10개의 선형 또는 분지형 알킬기, 탄소원자수 6-10개의 아릴기, 탄소원자수 1-10 개의 알콕시기, 탄소원자수 7-20 개의 아릴알킬기, 탄소원자수 1-10 개의 히드록시알킬기, 탄소원자수 2-20 개의 히드록시알콕시알킬기 또는 탄소원자수 3-10 개의 사이클로알킬기를 나타내고, R3은 탄소원자수 6-10개의 아릴기를 나타낸다.More specifically, in Formula 1, R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, Represents an alkoxy group having 1-10 carbon atoms, an arylalkyl group having 7-20 carbon atoms, a hydroxyalkyl group having 1-10 carbon atoms, a hydroxyalkoxyalkyl group having 2-20 carbon atoms, or a cycloalkyl group having 3-10 carbon atoms, R 3 represents an aryl group having 6-10 carbon atoms.
보다 더 구체적으로, 상기 화학식 1에서, R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-6개의 선형 또는 분지형 알킬기, 탄소원자수 6-10개의 아릴기, 탄소원자수 1-6 개의 알콕시기, 탄소원자수 7-16 개의 아릴알킬기, 탄소원자수 1-6 개의 히드록시알킬기, 탄소원자수 2-12 개의 히드록시알콕시알킬기 또는 탄소원자수 3-6 개의 사이클로알킬기를 나타내고, R3은 탄소원자수 6-10개의 아릴기를 나타낸다.More specifically, in Formula 1, R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-6 carbon atoms, an aryl group having 6-10 carbon atoms, Represents an alkoxy group having 1-6 carbon atoms, an arylalkyl group having 7-16 carbon atoms, a hydroxyalkyl group having 1-6 carbon atoms, a hydroxyalkoxyalkyl group having 2-12 carbon atoms, or a cycloalkyl group having 3-6 carbon atoms, R 3 represents an aryl group having 6-10 carbon atoms.
상기 화학식 1에서, 상기 선형 또는 분지형 알킬기, 아릴기, 알콕시기, 아릴알킬기, 히드록시알킬기, 히드록시알콕시알킬기, 사이클로알킬기는 각각 독립적으로 비치환되거나, 또는 할로겐, 탄소원자수 1-6개의 선형 또는 분지형 알킬기, 또는 탄소원자수 3-6 개의 사이클로알킬기에 의하여 치환될 수 있다.In Formula 1, the linear or branched alkyl group, aryl group, alkoxy group, arylalkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, and cycloalkyl group are each independently unsubstituted, or halogen, linear having 1-6 carbon atoms Or it may be substituted by a branched alkyl group or a cycloalkyl group having 3-6 carbon atoms.
본 발명의 일 구체예에 따르면, 상기 화학식 1에서, R1은 각각 독립적으로 수소, 메틸기, 에틸기, 프로필기 또는 부틸기이고; R2는 메틸기, 에틸기, 프로필기 또는 부틸기이며; R3은 페닐기이고; R4 내지 R10은 수소일 수 있다.According to an embodiment of the present invention, in Formula 1, R 1 is each independently hydrogen, methyl group, ethyl group, propyl group, or butyl group; R 2 is a methyl group, an ethyl group, a propyl group or a butyl group; R 3 is a phenyl group; R 4 to R 10 may be hydrogen.
상기 화학식 1로 표시되는 구조를 갖는 광중합 개시제는 본 발명의 감광성 수지 조성물에 우수한 잔막율 특성을 부여하며, 특히, R3 위치에 알킬기(예컨대, 메틸기, 에틸기 등)를 가지는 기존의 광중합 개시제에 비하여, 같은 미세 패턴 사이즈에서 월등히 우수한 잔막율 특성을 부여한다.The photopolymerization initiator having the structure represented by Formula 1 imparts excellent film retention properties to the photosensitive resin composition of the present invention, and in particular, compared to the conventional photopolymerization initiator having an alkyl group (eg, methyl group, ethyl group, etc.) at the R 3 position. , And provides excellent residual film rate characteristics at the same fine pattern size.
본 발명의 감광성 수지 조성물에는, 상기 (a) 알칼리 가용성 바인더 수지와 (b) 임의 성분인 광중합성 화합물의 합계 100 중량부를 기준으로, 상기 (c) 화학식 1의 광중합 개시제가 0.7내지 20 중량부의 양으로 포함된다. 본 발명의 감광성 수지 조성물에 포함되는 화학식 1의 광중합 개시제의 양이, (a) 알칼리 가용성 바인더 수지와 (b) 임의 성분인 광중합성 화합물의 합계 100 중량부를 기준으로, 0.7 중량부 미만이면 낮은 감도로 인하여 잔막율이 나빠지고 패턴 형성에 어려움이 있을 수 있으며, 20 중량부를 초과하면 보존 안정성에 문제가 발생할 수 있으며, 광중합 개시제의 용해도 감소로 인하여 박막 표면에 이물질을 발생시킬 수 있다.In the photosensitive resin composition of the present invention, based on the total of 100 parts by weight of the (a) alkali-soluble binder resin and (b) a photopolymerizable compound as an optional component, the (c) photopolymerization initiator of Formula 1 is in an amount of 0.7 to 20 parts by weight. Included as. Low sensitivity if the amount of the photopolymerization initiator of Formula 1 contained in the photosensitive resin composition of the present invention is less than 0.7 parts by weight based on 100 parts by weight of the total of (a) an alkali-soluble binder resin and (b) an optional photopolymerizable compound. Due to this, the residual film rate may be deteriorated and there may be difficulties in pattern formation. If it exceeds 20 parts by weight, a problem may occur in storage stability, and foreign matter may be generated on the surface of the thin film due to a decrease in solubility of the photopolymerization initiator.
일 구체예에서, 본 발명의 감광성 수지 조성물에 포함되는 화학식 1의 광중합 개시제의 양은, (a) 알칼리 가용성 바인더 수지와 (b) 광중합성 화합물의 합계 100 중량부를 기준으로, 0.8 중량부 이상, 0.9 중량부 이상, 1.0 중량부 이상, 1.1 중량부 이상, 1.2 중량부 이상, 1.4 중량부 이상, 1.6 중량부 이상 또는 1.8 중량부 이상일 수 있고, 또한 19.5 중량부 이하, 19 중량부 이하, 18.5 중량부 이하, 18 중량부 이하, 16 중량부 이하, 14 중량부 이하, 12 중량부 이하, 10 중량부 이하 또는 8 중량부 이하일 수 있다.In one embodiment, the amount of the photopolymerization initiator of Formula 1 included in the photosensitive resin composition of the present invention is 0.8 parts by weight or more, 0.9 parts by weight based on 100 parts by weight of the total of (a) alkali-soluble binder resin and (b) photopolymerizable compound. It may be at least 1.0 part by weight, at least 1.1 parts by weight, at least 1.2 parts by weight, at least 1.4 parts by weight, at least 1.6 parts by weight, or at least 1.8 parts by weight, and also 19.5 parts by weight or less, 19 parts by weight or less, 18.5 parts by weight It may be 18 parts by weight or less, 16 parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, or 8 parts by weight or less.
본 발명의 감광성 수지 조성물은, 상기 화학식 1의 광중합 개시제 이외에, 필요에 따라 추가의 광중합 개시제를 더 포함할 수 있다. 본 발명에서 추가로 사용 가능한 광중합 개시제로는 일반적으로 사용되는 트리아진계, 벤조인계, 아세토페논계, 이미다졸계, 크산톤계 또는 옥심에스테르계 등의 광개시제 화합물들을 들 수 있고, 보다 구체적으로는, 트리페닐포스핀옥사이드, 페닐비페닐케톤, 1-히드록시-1-벤조일시클로헥산, 벤질디메틸케탈, 1-벤질-1-디메틸아미노-1-(4-모폴리노-벤조일)프로판, 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판, 티옥산톤(thioxanthone), 1-클로로-4-프로필티옥산톤, 이소프로필티옥산톤, 디에틸티옥산톤, 에틸안트라퀴논, 4-벤조일-4-메틸디페닐설파이드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 벤조일포름산메틸, 1,7-비스(9-아크리디닐)헵탄, 9-n-부틸-3,6-비스(2-모폴리노-이소부틸로일)카바졸, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄온-1, 2-메틸-1-[(4-메틸티오)페닐]-2-모르폴리노프로판-1-온, 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸, 4,4'-비스(디에틸아미노)벤조페논, 2-머캅토벤조티아졸, 시바 스페셜 케미칼사의 Irgacure 369, Irgacure 379 Irgacur 651, Irgacure 907, Darocur TPO, Irgacure 819, OXE-01, OXE-02, 아데카사의 N-1919, NCI-831, 삼양사의 SPI-02, SPI-03, SPI-04, SPI-05 등을 들 수 있으나, 이에 한정되지는 않는다. 본 발명의 감광성 수지 조성물이 이러한 추가의 광중합 개시제를 포함하는 경우, 그 함량은 본 발명의 목적을 달성할 수 있는 범위 내에서 필요에 따라 적절하게 조절될 수 있다.The photosensitive resin composition of the present invention may further include, if necessary, an additional photopolymerization initiator in addition to the photopolymerization initiator of Formula 1 above. Photoinitiator compounds that can be additionally used in the present invention include commonly used photoinitiator compounds such as triazine-based, benzoin-based, acetophenone-based, imidazole-based, xanthone-based or oxime ester-based, and more specifically, triazine Phenylphosphine oxide, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzyldimethylketal, 1-benzyl-1-dimethylamino-1-(4-morpholino-benzoyl)propane, 2-mo Polyl-2-(4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propyl thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethylanthraquinone, 4- Benzoyl-4-methyldiphenylsulfide, benzoinbutyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4- Phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis (Trichloromethyl)-s-triazine, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[(4-methylthio)phenyl ]-2-morpholinopropan-1-one, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 4,4'-bis(diethylamino)benzophenone, 2-mercaptobenzothiazole, Irgacure 369, Irgacure 379 Irgacur 651 from Ciba Special Chemicals, Irgacure 907, Darocur TPO, Irgacure 819, OXE-01, OXE-02 , Adeka's N-1919, NCI-831, Samyang's SPI-02, SPI-03, SPI-04, SPI-05, etc., but are not limited thereto. When the photosensitive resin composition of the present invention contains such an additional photopolymerization initiator, the content may be appropriately adjusted as necessary within a range capable of achieving the object of the present invention.
본 발명의 감광성 수지 조성물은 (d) 유기 용매를 포함한다.The photosensitive resin composition of this invention contains (d) an organic solvent.
상기 유기 용매로는, 예컨대, 메탄올, 에탄올 등의 알코올류; 디클로로에틸 에테르, n-부틸 에테르, 디이소아밀 에테르,메틸페닐 에테르, 테트라히드로퓨란 등의 에테르류; 에틸렌 글리콜 모노메틸에테르, 에틸렌 글리콜 모노에틸에테르 등의 글리콜 에테르류; 메틸 셀로솔브 아세테이트, 에틸 셀로솔브 아세테이트, 디에틸 셀로솔브 아세테이트 등의 셀로솔브 아세테이트류; 메틸에틸 카르비톨, 디에틸 카르비톨, 디에틸렌 글리콜 모노메틸에테르, 디에틸렌 글리콜 모노에틸에테르, 디에틸렌 글리콜 디메틸에테르, 디에틸렌 글리콜 메틸에틸에테르, 디에틸렌 글리콜 디에틸에테르 등의 카르비톨류; 프로필렌 글리콜 메틸에테르 아세테이트, 프로필렌 글리콜 프로필에테르 아세테이트 등의 프로필렌 글리콜 알킬에테르 아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 메틸에틸케톤, 사이클로헥사논, 4-히드록시-4-메틸-2-펜타논, 메틸-n-프로필케톤, 메틸-n-부틸케톤, 메틸-n-아밀케톤, 2-헵타논 등의 케톤류; 초산 에틸, 초산-n-부틸, 초산 이소부틸 등의 포화 지방족 모노카르복실산 알킬 에스테르류; 젖산 메틸, 젖산 에틸 등의 젖산 에스테르류; 옥시 초산 메틸, 옥시 초산 에틸, 옥시 초산 부틸 등의 옥시 초산 알킬 에스테르류; 메톡시 초산 메틸, 메톡시 초산 에틸, 메톡시 초산 부틸, 에톡시 초산 메틸, 에톡시 초산 에틸 등의 알콕시 초산 알킬 에스테르류; 3-옥시 프로피온산 메틸, 3-옥시 프로피온산 에틸 등의 3-옥시 프로피온산 알킬에스테르류; 3-메톡시 프로피온산 메틸, 3-메톡시 프로피온산 에틸, 3-에톡시 프로피온산 에틸, 3-에톡시 프로피온산 메틸 등의 3-알콕시 프로피온산 알킬 에스테르류; 2-옥시 프로피온산 메틸, 2-옥시 프로피온산 에틸, 2-옥시 프로피온산 프로필 등의 2-옥시 프로피온산 알킬 에스테르류; 2-메톡시 프로피온산메틸, 2-메톡시 프로피온산 에틸, 2-에톡시 프로피온산 에틸, 2-에톡시 프로피온산 메틸 등의 2-알콕시 프로피온산 알킬 에스테르류; 2-옥시-2-메틸 프로피온산 메틸, 2-옥시-2-메틸 프로피온산 에틸 등의 2-옥시-2-메틸프로피온산 에스테르류, 2-메톡시-2-메틸 프로피온산 메틸, 2-에톡시-2-메틸 프로피온산 에틸 등의 2-알콕시-2-메틸 프로피온산 알킬류의 모노옥시 모노카르복실산 알킬 에스테르류; 2-히드록시 프로피온산 에틸, 2-히드록시-2-메틸 프로피온산 에틸, 히드록시 초산 에틸, 2-히드록시-3-메틸 부탄산 메틸 등의 에스테르류; 피루빈산 에틸 등의 케톤산 에스테르류 등을 들 수 있으며, 또한, N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸포름아닐리드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 디메틸술폭시드, 벤질에틸에테르, 디헥실에테르, 아세틸아세톤, 이소포론, 카프론산, 카프릴산, 1-옥탄올, 1-노난올, 벤질알코올, 초산 벤질, 안식향산 에틸, 옥살산 디에틸, 말레인산 디에틸, γ-부티로락톤, 탄산 에틸렌, 탄산 프로필렌, 페닐 셀로솔브 아세테이트 등을 들 수 있다. 상기 한 것들 중에서 선택된 용매를 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.Examples of the organic solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl methoxy acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionic acid propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methylpropionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, and the like. Further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetate Amide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. Solvents selected from the above can be used alone or in combination of two or more.
본 발명의 감광성 수지 조성물에 있어서, 상기 유기 용매의 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 30 중량부 이상, 35 중량부 이상, 40 중량부 이상, 45 중량부 이상 또는 50 중량부 이상일 수 있고, 또한 90 중량부 이하, 85 중량부 이하, 80 중량부 이하, 75 중량부 이하 또는 70 중량부 이하일 수 있으나, 이에 한정되는 것은 아니다. 본 발명의 감광성 수지 조성물의 고형분 농도에는 특별한 제한이 없으며, 일 구체예에서, 고형분 농도는 10내지 50중량%일 수 있으나, 이에 한정되지 않는다.In the photosensitive resin composition of the present invention, the content of the organic solvent can be appropriately adjusted as necessary, for example, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight based on the total 100 parts by weight of the composition. It may be greater than or equal to 50 parts by weight, and may be 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less, but is not limited thereto. There is no particular limitation on the solid content concentration of the photosensitive resin composition of the present invention, and in one embodiment, the solid content concentration may be 10 to 50% by weight, but is not limited thereto.
일 구체예에서, 본 발명의 감광성 수지 조성물은 분자량 조절을 위한 연쇄이동제를 추가로 포함할 수 있다.In one embodiment, the photosensitive resin composition of the present invention may further include a chain transfer agent for controlling molecular weight.
일 구체예에서, 분자량 조절을 위한 연쇄이동제로는 황원자 함유 화합물이 사용될 수 있다. 상기 황원자 함유 연쇄이동제는, 예를 들면, 티오글리콜산, 티오말산, 티오살리칠산, 2-메르캅토프로피온산, 3-메르캅토프로피온산, 3-메르캅토낙산, N-(2-메르캅토프로피오닐)글리신, 2-메르캅토니코틴산, 3-[N-(2-메르캅토에틸)카르바모일]프로피온산, 3-[N-(2-메르캅토에틸)아미노]프로피온산, N-(3-메르캅토프로피오닐)알라닌, 2-메르캅토에탄술폰산, 3-메르캅토프로판술폰산, 4-메르캅토부탄술폰산, 도데실(4-메틸티오)페닐에테르, 2-메르캅토에탄올, 3-메르캅토-1,2-프로판디올, 1-메르캅토-2-프로판올, 3-메르캅토-2-부탄올, 메르캅토페놀, 2-메르캅토에틸아민, 2-메르캅토이미다졸, 2-메르캅토벤조이미다졸, 2-메르캅토-3-피리디놀, 2-메르캅토벤조티아졸, 메르캅토아세트산, 트리메틸롤프로판 트리스(3-메르캅토프로피오네이트), 펜타에리스리톨 테트라키스(3-메르캅토프로피오닉아세트산, 도데칸티올, 2,4-디페닐-4-메틸-1-펜텐, 옥탄티올, 2-머캅토에탄올 등의 티올류, 또는 이들의 조합으로부터 선택된 것일 수 있으나, 이에 한정되지 않는다.In one embodiment, a sulfur atom-containing compound may be used as a chain transfer agent for molecular weight control. The sulfur atom-containing chain transfer agent, for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl) Glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropi) O'Nyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2 -Propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2 -Mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionic acetic acid, dodecane) Thiol, 2,4-diphenyl-4-methyl-1-pentene, octanthiol, 2-mercaptoethanol, and other thiols, or a combination thereof may be selected from, but is not limited thereto.
본 발명의 감광성 수지 조성물에 상기 연쇄이동제가 포함될 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 0.1 내지 10중량부의 양으로, 보다 구체적으로는 0.2 내지 5중량부, 보다 더 구체적으로는 0.5 내지 2 중량부의 양으로 포함될 수 있으나, 이에 한정되지는 않는다.When the chain transfer agent is included in the photosensitive resin composition of the present invention, the content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 5 parts by weight, more specifically 0.5 to 2 parts by weight, but is not limited thereto.
또한, 일 구체예에서, 본 발명의 감광성 수지 조성물은 필요에 따라 선택적으로, 충전제, 그 밖의 고분자 화합물, 열라디칼 발생제, 자외선흡수제, 밀착촉진제, 중합 조절제, pH 조절제, 스케일 방지제, 전해질 등, 해당 기술분야에 있어서 공지된 첨가제를 추가로 함유할 수 있다. 이들 추가의 첨가제 종류 및 함량은 특별히 제한되지 않고 당업계에서 공지된 통상의 종류 및 함량으로 사용할 수 있다.In addition, in one embodiment, the photosensitive resin composition of the present invention optionally includes a filler, other polymer compounds, thermal radical generators, ultraviolet absorbers, adhesion promoters, polymerization regulators, pH regulators, scale inhibitors, electrolytes, etc. It may further contain additives known in the art. The types and contents of these additional additives are not particularly limited and may be used in conventional types and contents known in the art.
본 발명의 감광성 조성물은, 상기한 성분들 이외에, 필요에 따라 하나 이상의 추가 성분, 예컨대, 착색제, 보조경화제, 접착 보조제, 및/또는 계면활성제를 더 포함할 수 있다.In addition to the above components, the photosensitive composition of the present invention may further include one or more additional components, such as a colorant, a co-curing agent, an adhesion aid, and/or a surfactant, if necessary.
상기 착색제는 유기 안료, 염료, 또는 이들의 조합을 포함할 수 있다. 상기 유기 안료는 적색안료, 녹색안료, 청색 안료 및 황색 안료로 이루어진 군에서 선택된 하나 또는 2종 이상의 혼합물일 수 있다. 또한, 흑색 착색제로서 흑색 무기 착색제, 흑색 유기 착색제 또는 이들의 혼합물이 포함될 수 있다.The colorant may include an organic pigment, a dye, or a combination thereof. The organic pigment may be one or a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment. Further, as the black colorant, a black inorganic colorant, a black organic colorant, or a mixture thereof may be included.
상기 적색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 적색 안료 179, C.I. 적색 안료 254, C.I. 적색 안료255, C.I. 적색 안료 264, C.I. 적색 안료 270, C.I. 적색 안료 272, C.I. 적색 안료 177, C.I. 적색 안료 89등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The red pigment is C.I. in the Color Index. Red pigment 179, C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89, etc. may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
상기 녹색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 녹색 안료 59, C.I. 녹색 안료 58, C.I. 녹색 안료36, C.I. 녹색 안료 7 등과 같은 할로겐이 치환된 구리 프탈로시아닌 안료 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The green pigment is C.I. in the Color Index. Green pigment 59, C.I. Green pigment 58, C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
상기 청색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 청색 안료 15:6, C.I. 청색 안료 15:0, C.I. 청색 안료 15:1, C.I. 청색 안료 15:2, C.I. 청색 안료 15:3, C.I. 청색 안료 15:4, C.I. 청색 안료 15:5, C.I 청색안료 15:6, C.I. 청색 안료 16 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.The blue pigment is C.I. in the Color Index. Blue pigment 15:6, C.I. Blue pigment 15:0, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I blue pigment 15:6, C.I. Blue pigment 16 may be used, and these may be used alone or in combination of two or more, but are not limited thereto.
상기 황색 안료는 컬러 인덱스(Color Index) 내에서 C.I. 황색 안료 139 등과 같은 이소인돌린계 안료, C.I. 황색 안료 138 등과 같은 퀴노프탈론계 안료, C.I. 황색 안료 150 등과 같은 니켈 컴플렉스 안료, C.I. 황색 안료100 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는것은 아니다.The yellow pigment is C.I. in the Color Index. Isoindolin-based pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. Nickel complex pigments such as yellow pigment 150, C.I. Yellow pigment 100 or the like 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 흑색 무기 착색제의 구체적인 예로는, 카본블랙, 티타늄 블랙, Cu-Fe-Mn-계 산화물 및 합성 철 블랙과 같은 금속 산화물 등을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.As a specific example of the black inorganic colorant, carbon black, titanium black, Cu-Fe-Mn-based oxide, and metal oxide such as synthetic iron black may be used, and these may be used alone or in combination of two or more, It is not necessarily limited thereto.
상기 흑색유기 착색제의 구체적인 예로는 아닐린 블랙, 락탐 블랙, 페릴렌 블랙 등을 들 수 있고, 그 중에서도 락탐 블랙(예: 바스프사의 Black 582 등)을 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다.Specific examples of the black organic colorant include aniline black, lactam black, and perylene black, among which lactam black (eg, BASF's Black 582, etc.) may be used, and these may be used alone or in combination of two or more. It can be used, but is not necessarily limited thereto.
상기 착색제로 안료를 사용할 경우, 안료를 분산시키기 위해서 분산제, 공중합체 수지, 용매 등과 혼합된 착색 분산액(mill base)의 형태로 착색 감광성 수지 조성물에 첨가될 수 있다. When a pigment is used as the colorant, it may be added to the colored photosensitive resin composition in the form of a colored dispersion (mill base) mixed with a dispersant, a copolymer resin, a solvent, etc. to disperse the pigment.
본 발명의 감광성 수지 조성물에 상기 착색제가 포함될 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 1 내지 40중량부의 양으로, 보다 구체적으로는 2 내지 20중량부, 보다 더 구체적으로는 5 내지 10 중량부의 양으로 포함될 수 있으나, 이에 한정되지는 않는다.When the colorant is included in the photosensitive resin composition of the present invention, the content may be appropriately adjusted as necessary, for example, in an amount of 1 to 40 parts by weight, more specifically 2 to 20 parts by weight based on the total 100 parts by weight of the composition. Parts by weight, and more specifically, may be included in an amount of 5 to 10 parts by weight, but is not limited thereto.
상기 보조경화제는 광개시제의 라디칼 생성 및 박막의 경화도를 증진시키는 작용을 하며, 그 예로는 펜타에리스리톨 테트라키스(3-머캅토프로피오네이트), 디옥틸프탈레이트, 디이소노닐프탈레이트, 디옥틸아디페이트, 트리크레실포스페이트, 및 2,2,4-트리메틸-1,3-펜탄디올 모노이소부티레이트, 2-머캡토벤조이미다졸, 2-머캡토벤조티아졸, 2-머캡토벤조옥사졸, 2,5,-디머캡토-1,3,4-티아디아졸, 2-머캡토-4,6-디메틸아미노피리딘 등을 들 수 있고, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다. 본 발명의 감광성 수지 조성물에 상기 보조경화제가 포함될 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 0.1 내지 10 중량부의 양으로, 보다 구체적으로는 0.2 내지 8 중량부, 보다 더 구체적으로는 0.4 내지 5 중량부의 양으로 포함될 수 있으나, 이에 한정되지는 않는다.The auxiliary curing agent acts to generate radicals of the photoinitiator and enhance the degree of curing of the thin film, examples of which include pentaerythritol tetrakis (3-mercaptopropionate), dioctylphthalate, diisononylphthalate, dioctyl adipate, Tricresylphosphate, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2, 5,-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, and the like, and these may be used alone or in combination of two or more, but must be limited thereto It does not become. When the auxiliary curing agent is included in the photosensitive resin composition of the present invention, its content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 8 parts by weight, more specifically 0.4 to 5 parts by weight, but is not limited thereto.
상기 접착 보조제는 기판과의 접착성을 향상시키는 작용을 하며, 기판과의 밀착성 등을 개선하기 위해 비닐기, 카르복실기, 메타크릴옥시기, 이소시아네이트기, 에폭시기 등의 반응성 치환기를 가질 수 있다. 상기 접착 보조제의 예로는, 트리메톡시실릴 벤조산, γ-메타크릴옥시프로필 트리메톡시실란, 비닐 트리아세톡시실란, 비닐 트리메톡시실란, γ-이소 시아네이트 프로필 트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리메톡시실란 등을 등을 들 수 있고, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 반드시 한정되는 것은 아니다. 본 발명의 감광성 수지 조성물에 상기 접착 보조제가 포함될 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 0.1 내지 10 중량부의 양으로, 보다 구체적으로는 0.2 내지 8 중량부, 보다 더 구체적으로는 0.4 내지 5 중량부의 양으로 포함될 수 있으나, 이에 한정되지는 않는다.The adhesion aid may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate and the like. Examples of the adhesion aids include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-gly Cidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. may be mentioned, and these may be used alone or in combination of two or more, but are limited thereto. no. When the adhesive auxiliary agent is included in the photosensitive resin composition of the present invention, the content can be appropriately adjusted as necessary, for example, in an amount of 0.1 to 10 parts by weight, more specifically 0.2 to It may be included in an amount of 8 parts by weight, more specifically 0.4 to 5 parts by weight, but is not limited thereto.
상기 계면활성제는 감광성 수지 조성물의 코팅성이나 현상성을 향상시키는 작용을 하며, 그 종류는 특별히 한정되지 않고, 예를 들어 불소계 계면활성제 또는 실리콘 계면활성제일 수 있다. 불소계 계면활성제의 시판품으로는, BM-1000, BM-1100(BM Chemie社), 프로라이드 FC-135/FC-170C/FC-430(스미토모 쓰리엠㈜), SH-28PA/-190/SZ-6032(도레 시리콘㈜) 등이 있다. 실리콘 계면활성제의 시판품으로는 BYK사의 BYK-310, BYK-313, BYK-320, BYK-333 등이 있으나, 이에 반드시 한정되는 것은 아니다. 본 발명의 감광성 수지 조성물에 상기 계면활성제가 포함될 경우, 그 함량은 필요에 따라 적절하게 조절할 수 있으며, 예를 들면 조성물 총 100 중량부에 대하여 0.01 내지 5 중량부의 양으로, 보다 구체적으로는 0.02 내지 4 중량부, 보다 더 구체적으로는 0.05 내지 2 중량부의 양으로 포함될 수 있으나, 이에 한정되지는 않는다.The surfactant serves to improve the coatability or developability of the photosensitive resin composition, and the type is not particularly limited, and may be, for example, a fluorine-based surfactant or a silicone surfactant. Commercially available fluorine-based surfactants include BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M), SH-28PA/-190/SZ-6032 (Tore Silicon Co., Ltd.). Commercially available products of the silicone surfactant include BYK's BYK-310, BYK-313, BYK-320, BYK-333, and the like, but are not limited thereto. When the surfactant is included in the photosensitive resin composition of the present invention, the content can be appropriately adjusted as needed, for example, in an amount of 0.01 to 5 parts by weight, more specifically 0.02 to It may be included in an amount of 4 parts by weight, more specifically 0.05 to 2 parts by weight, but is not limited thereto.
본 발명의 감광성 수지 조성물은 미세 패턴을 구현할 수 있는 동시에, 잔막율을 높일 수 있어, 컬럼 스페이서, 블랙 매트릭스, 또는 착색(예컨대, 블랙) 컬럼 스페이서를 형성하는 데에 적합하기 때문에, OLED 디스플레이 및 TFT-LCD 패널을 비롯한 다양한 전자 부품에 사용될 수 있다.The photosensitive resin composition of the present invention is suitable for forming a column spacer, a black matrix, or a colored (e.g., black) column spacer, as it can realize a fine pattern and increase the residual film rate. -Can be used for various electronic parts including LCD panels.
따라서, 본 발명의 또 다른 측면에 따르면, 본 발명의 감광성 수지 조성물로부터 형성되는 미세 패턴화 경화물이 제공된다.Accordingly, according to another aspect of the present invention, a fine patterned cured product formed from the photosensitive resin composition of the present invention is provided.
일 구체예에서, 상기 미세 패턴화 경화물은 컬럼 스페이서, 블랙 매트릭스, 또는 착색(예컨대, 블랙) 컬럼 스페이서일 수 있다.In one embodiment, the finely patterned cured product may be a column spacer, a black matrix, or a colored (eg, black) column spacer.
상기 미세 패턴화 경화물은, 예컨대, 본 발명의 감광성 수지 조성물을 기판 상에 도포한 뒤, 패턴화 노광 및 현상하는 방법에 의하여 형성될 수 있으나, 이에 한정되는 것은 아니다.The fine patterned cured product may be formed by, for example, applying the photosensitive resin composition of the present invention onto a substrate, followed by patterning exposure and development, but is not limited thereto.
이하, 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 본 발명의 범위는 이들 실시예로 한정되지 않는다.Hereinafter, the present invention will be described in more detail through examples. However, the scope of the present invention is not limited to these examples.
[실시예][Example]
제조예: 바인더 수지 제조Manufacturing Example: Binder Resin Manufacturing
메타크릴산,메틸메타크릴산, 메틸메타크릴레이트, 글리시딜메타크릴레이트 및 벤질아클릴레이트를 각각 020:30:30:20의 몰비로 혼합한 단량체 혼합물 30 중량부, 열 개시제로서 V-65(Wako Chemical사) 1 중량부, 분자량 조절을 위한 연쇄이동제로서 3-메르캅토프로피온산(3-Mercaptopropionic acid) 1중량부, 및 유기 용매로서 메틸 3-메톡시프로피오네이트 68중량부를 반응 용기에 넣은 후, 질소 분위기 하에서 65℃를 유지하며 8시간 동안 교반하며 중합시켜 바인더 수지로서 아크릴 중합체를 제조하였다. 상기 제조된 아크릴 중합체의 중량 평균분자량은 25,000이었다.30 parts by weight of a monomer mixture obtained by mixing methacrylic acid, methyl methacrylic acid, methyl methacrylate, glycidyl methacrylate and benzyl acrylate at a molar ratio of 020:30:30:20, respectively, as a thermal initiator V- 65 (Wako Chemical) 1 part by weight, 3-mercaptopropionic acid as a chain transfer agent for molecular weight control, 1 part by weight, and methyl 3-methoxypropionate as an organic solvent 68 parts by weight in a reaction vessel After the addition, the mixture was polymerized while maintaining at 65° C. under a nitrogen atmosphere and stirring for 8 hours to prepare an acrylic polymer as a binder resin. The weight average molecular weight of the prepared acrylic polymer was 25,000.
실시예 1 내지 5 및 비교예 1 내지 9: 감광성 수지 조성물의 제조Examples 1 to 5 and Comparative Examples 1 to 9: Preparation of photosensitive resin composition
자외선 차단막과 교반기가 설치되어 있는 반응혼합조에 하기 표 1의 조성에 따라서 바인더 수지(13 중량부), 불포화 결합을 갖는 중합성 화합물(26 중량부), 광중합 개시제 및 용매(60 중량부)를 첨가하고, 상온에서 교반하여 혼합하였다. 이후, 혼합된 용액을 0.5 마이크론 크기의 필터를 이용하여 여과하여 감광성 수지 조성물을 제조하였다.According to the composition of Table 1 below, a binder resin (13 parts by weight), a polymerizable compound having an unsaturated bond (26 parts by weight), a photopolymerization initiator and a solvent (60 parts by weight) were added to the reaction mixing tank equipped with a UV blocking film and a stirrer. And stirred at room temperature to mix. Thereafter, the mixed solution was filtered using a 0.5 micron filter to prepare a photosensitive resin composition.
<사용된 조성물 성분들에 대한 설명><Description of the components of the composition used>
바인더 수지: 제조예에서 수득된 아크릴 중합체Binder resin: acrylic polymer obtained in Preparation Example
DPHA: dipentaerythritol hexaacrylateDPHA: dipentaerythritol hexaacrylate
[광개시제 A][Photoinitiator A]
[광개시제 B][Photoinitiator B]
[광개시제 C][Photoinitiator C]
[OXE-01][OXE-01]
용매: 메틸 3-메톡시프로피오네이트(MMP)Solvent: methyl 3-methoxypropionate (MMP)
[표 1][Table 1]
상기 제조된 실시예 및 비교예의 감광성 수지 조성물들 각각을 글래스 위에 약 1.0~15.0 마이크로 두께로 코팅한 후, 1.0~0.5 torr의 저압 하에 코팅면에 있는 용매를 1차로 제거하고, 이후, 80~110℃ 핫플레이트 위에서 약 30~120 초 동안 두어 잔류하는 용매를 제거하였다. After coating each of the photosensitive resin compositions of Examples and Comparative Examples prepared above to a thickness of about 1.0 to 15.0 microns on glass, the solvent on the coating surface was firstly removed under a low pressure of 1.0 to 0.5 torr, and then, 80 to 110 The remaining solvent was removed by placing it on a hot plate at ℃ for about 30 to 120 seconds.
상기와 같이 하여 준비된 박막을 노광하고, 노광된 박막을 알카리 수용액(테트라메틸암모늄히드록시드)으로 현상한 후, 형성된 패턴을 150-250℃의 오븐에서 30-90 분간 가열처리하여, 미세 패턴을 가지는 최종 경화막을 얻었다.After exposing the thin film prepared as described above, developing the exposed thin film with an alkaline aqueous solution (tetramethylammonium hydroxide), the formed pattern was heat-treated in an oven at 150-250° C. for 30-90 minutes, thereby forming a fine pattern. Eggplant obtained the final cured film.
상기 얻어진 실시예 및 비교예 각각의 패턴에 대하여 다음과 같은 항목들을 평가하였다.The following items were evaluated for each pattern of the obtained Examples and Comparative Examples.
1) 패턴 크기1) pattern size
SNU사의 SNU장비를 이용하여 상기 제조된 패턴의 크기를 측정하였다. The size of the prepared pattern was measured using SNU's SNU equipment.
2) 잔막율2) film remaining rate
상기 경화막 제조방법에서 마스크를 개재하지 않고 실시하였으며 노광하기 전의 박막 두께와 최종 경화막의 두께 변화 비율을 계산하여 잔막율로 하였다. In the method of manufacturing the cured film, the film thickness before exposure and the rate of change in the thickness of the final cured film were calculated as the residual film rate.
잔막율 (%) = [경화후 두께 / 노광전 두께] * 100Remaining film rate (%) = [Thickness after curing / thickness before exposure] * 100
상기 항목들의 평가 결과를 하기 표 2에 나타내었다.The evaluation results of the above items are shown in Table 2 below.
[표 2] [Table 2]
상기 표 2로부터 알 수 있듯이, 실시예와 비교예의 조성물들을 대비하였을 때, 도 1에 나타낸 바와 같이, 동일한 패턴 크기에서 실시예의 조성물들이 비교예에 비하여 보다 우수한 잔막율을 나타내었다.As can be seen from Table 2, when the compositions of the Example and the Comparative Example were compared, as shown in FIG. 1, the compositions of the Example showed a better residual film ratio than the Comparative Example in the same pattern size.
또한 광개시제 C는, 그와 동일한 라디칼을 생성하면서 기존에 많이 사용하고 있는 OXE-01(비교예7)에 비해서 높은 잔막율을 형성하고 있으며, 이는 도 2에 나타낸 바와 같이, 광개시제 C가 I-line의 빛을 흡수하는 면적이 OXE-01 보다 넓기 때문으로 여겨진다.In addition, photoinitiator C has a higher residual film rate than OXE-01 (Comparative Example 7), which is widely used in the past while generating the same radicals, which is shown in FIG. This is believed to be because the area that absorbs light of OXE-01 is larger than that of OXE-01.
Claims (10)
- (a) 알칼리 가용성 바인더 수지; (a) alkali-soluble binder resin;(b) 임의로 광중합성 화합물; (b) optionally a photopolymerizable compound;(c) 하기 화학식 1로 표시되는 구조를 갖는 광중합 개시제; 및 (c) a photopolymerization initiator having a structure represented by the following formula (1); And(d) 유기 용매;를 포함하며, (d) an organic solvent; and,상기 (a) 알칼리 가용성 바인더 수지와 (b) 임의로 광중합성 화합물의 합계 100 중량부를 기준으로, 상기 (c) 광중합 개시제 0.7 내지 20 중량부를 포함하는, 감광성 수지 조성물:A photosensitive resin composition comprising 0.7 to 20 parts by weight of the (c) photopolymerization initiator based on the total of 100 parts by weight of the (a) alkali-soluble binder resin and (b) optionally a photopolymerizable compound:[화학식 1][Formula 1]상기 화학식 1에서,In Formula 1,R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-20개의 선형 또는 분지형 알킬기, 탄소원자수 6-20개의 아릴기, 탄소원자수 1-20 개의 알콕시기, 탄소원자수 7-40 개의 아릴알킬기, 탄소원자수 1-20 개의 히드록시알킬기, 탄소원자수 2-40 개의 히드록시알콕시알킬기 또는 탄소원자수 3-20 개의 사이클로알킬기를 나타내고,R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, a carbon source Embroidery 7-40 arylalkyl groups, 1-20 carbon atoms hydroxyalkyl groups, 2-40 carbon atoms hydroxyalkoxyalkyl groups or 3-20 carbon atoms cycloalkyl group,R3은 탄소원자수 6-20개의 아릴기를 나타낸다.R 3 represents an aryl group having 6-20 carbon atoms.
- 제1항에 있어서, 상기 알칼리 가용성 바인더 수지가 아크릴 중합체 또는 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체, 또는 노볼락 또는 비스페놀 타입의 알칼리 가용성 중합체를 포함하는 감광성 수지 조성물.The photosensitive resin composition according to claim 1, wherein the alkali-soluble binder resin contains an acrylic polymer, an acrylic polymer having an acrylic unsaturated bond in a side chain, or a novolac or bisphenol type alkali-soluble polymer.
- 제1항에 있어서, 상기 광중합성 화합물이 적어도 2 개 이상의 에틸렌계 이중 결합을 가지는 가교성 모노머인, 감광성 수지 조성물.The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound is a crosslinkable monomer having at least two or more ethylenic double bonds.
- 제1항에 있어서, R1, R2 및 R4 내지 R10은 각각 독립적으로 수소, 할로겐, 탄소원자수 1-10개의 선형 또는 분지형 알킬기, 탄소원자수 6-10개의 아릴기, 탄소원자수 1-10 개의 알콕시기, 탄소원자수 7-20 개의 아릴알킬기, 탄소원자수 1-10 개의 히드록시알킬기, 탄소원자수 2-20 개의 히드록시알콕시알킬기 또는 탄소원자수 3-10 개의 사이클로알킬기를 나타내고, R3은 탄소원자수 6-10개의 아릴기인, 감광성 수지 조성물.The method of claim 1 , wherein R 1 , R 2 and R 4 to R 10 are each independently hydrogen, halogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon atom number 1- 10 alkoxy groups, 7-20 carbon atoms arylalkyl groups, 1-10 carbon atoms hydroxyalkyl groups, 2-20 carbon atoms hydroxyalkoxyalkyl groups or 3-10 carbon atoms cycloalkyl groups, R 3 is a carbon source Embroidered 6-10 aryl groups, photosensitive resin composition.
- 제1항에 있어서, 상기 화학식 1에서, R1은 각각 독립적으로 수소, 메틸기, 에틸기, 프로필기 또는 부틸기이고; R2는 메틸기, 에틸기, 프로필기 또는 부틸기이며; R3은 페닐기이고; R4 내지 R10은 수소인, 감광성 수지 조성물.The method of claim 1, wherein in Formula 1, R 1 is each independently hydrogen, methyl group, ethyl group, propyl group, or butyl group; R 2 is a methyl group, an ethyl group, a propyl group or a butyl group; R 3 is a phenyl group; R 4 to R 10 are hydrogen, the photosensitive resin composition.
- 제1항에 있어서, 연쇄이동제를 추가로 포함하는, 감광성 수지 조성물.The photosensitive resin composition according to claim 1, further comprising a chain transfer agent.
- 제6항에 있어서, 상기 연쇄이동제가 티오글리콜산, 티오말산, 티오살리칠산, 2-메르캅토프로피온산, 3-메르캅토프로피온산, 3-메르캅토낙산, N-(2-메르캅토프로피오닐)글리신, 2-메르캅토니코틴산, 3-[N-(2-메르캅토에틸)카르바모일]프로피온산, 3-[N-(2-메르캅토에틸)아미노]프로피온산, N-(3-메르캅토프로피오닐)알라닌, 2-메르캅토에탄술폰산, 3-메르캅토프로판술폰산, 4-메르캅토부탄술폰산, 도데실(4-메틸티오)페닐에테르, 2-메르캅토에탄올, 3-메르캅토-1,2-프로판디올, 1-메르캅토-2-프로판올, 3-메르캅토-2-부탄올, 메르캅토페놀, 2-메르캅토에틸아민, 2-메르캅토이미다졸, 2-메르캅토벤조이미다졸, 2-메르캅토-3-피리디놀, 2-메르캅토벤조티아졸, 메르캅토아세트산, 트리메틸롤프로판 트리스(3-메르캅토프로피오네이트), 펜타에리스리톨 테트라키스(3-메르캅토프로피오닉아세트산, 도데칸티올, 2,4-디페닐-4-메틸-1-펜텐, 옥탄티올, 2-머캅토에탄올, 또는 이들의 조합으로부터 선택되는, 감광성 수지 조성물.The method of claim 6, wherein the chain transfer agent is thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine. , 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl ) Alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2- Propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2- Mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionic acetic acid, dodecanthiol) , 2,4-diphenyl-4-methyl-1-pentene, octanthiol, 2-mercaptoethanol, or a photosensitive resin composition selected from a combination thereof.
- 제1항에 있어서, 착색제, 보조경화제, 접착 보조제 및 계면활성제로부터 선택되는 하나 이상의 성분을 더 포함하는, 감광성 수지 조성물.The photosensitive resin composition according to claim 1, further comprising at least one component selected from a colorant, a co-curing agent, an adhesion aid, and a surfactant.
- 제1항 내지 제8항 중 어느 한 항의 감광성 수지 조성물로부터 형성되는 경화물.A cured product formed from the photosensitive resin composition according to any one of claims 1 to 8.
- 제9항에 있어서, 경화물이 컬럼 스페이서, 블랙 매트릭스, 또는 착색 컬럼 스페이서인, 경화물.The cured product according to claim 9, wherein the cured product is a column spacer, a black matrix, or a colored column spacer.
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JP6464764B2 (en) * | 2015-01-16 | 2019-02-06 | Jsr株式会社 | Radiation-sensitive coloring composition, spacer, method for forming the same, and liquid crystal display device |
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KR102254366B1 (en) * | 2017-03-28 | 2021-05-24 | 도레이 카부시키가이샤 | Photosensitive resin composition, cured film, element provided with cured film, organic EL display device provided with cured film, method for producing cured film, and method for producing organic EL display device |
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KR20170032372A (en) * | 2014-07-15 | 2017-03-22 | 도쿄 오카 고교 가부시키가이샤 | Photosensitive composition and compound |
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