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WO2013012230A2 - Light curable resin composition - Google Patents

Light curable resin composition Download PDF

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Publication number
WO2013012230A2
WO2013012230A2 PCT/KR2012/005657 KR2012005657W WO2013012230A2 WO 2013012230 A2 WO2013012230 A2 WO 2013012230A2 KR 2012005657 W KR2012005657 W KR 2012005657W WO 2013012230 A2 WO2013012230 A2 WO 2013012230A2
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WO
WIPO (PCT)
Prior art keywords
group
methacrylate
acrylate
resin composition
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2012/005657
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French (fr)
Korean (ko)
Other versions
WO2013012230A3 (en
Inventor
남동진
김두식
김병욱
박경민
유재원
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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Publication of WO2013012230A2 publication Critical patent/WO2013012230A2/en
Publication of WO2013012230A3 publication Critical patent/WO2013012230A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate

Definitions

  • the present invention relates to a photocurable resin composition, and more particularly, can be applied to a mold for imprint lithography to prevent expensive original stamps from being damaged due to excellent release properties with the original stamp, regardless of whether a release agent is treated on the original stamp surface.
  • the present invention relates to a photocurable resin composition which is excellent in chemical resistance and durability, and can more quickly and stably produce fine patterns required for manufacturing various electronic devices including semiconductors and displays.
  • a pattern forming target material is formed into a thin film on a semiconductor wafer or a glass substrate, the photoresist is applied thereon, the mask on which the desired pattern is formed is covered, the photoresist is exposed to light and then exposed.
  • a photoresist pattern is formed on the substrate in the shape of a designed mask pattern by removing the photoresist of the exposed portion (positive photoresist) or the unexposed portion (negative photoresist) using a developer, and then the photoresist pattern is formed.
  • a pattern of the initial deposition material is formed by finally removing the photoresist that used as a mask for the etching solution using a stripper.
  • a photoresist method has a problem in that manufacturing cost increases and productivity decreases due to the limitation of resolution, many processes, long process time, and expensive equipment used in the process.
  • Nanoimprint lithography is a nanodevice fabrication method introduced by Professor Chou of Princeton University in the mid-1990s. It is attracting attention as a technology to replace low-productivity electron beam lithography or expensive optical lithography.
  • Nanoimprint lithography process can be largely divided into heat processing method and pattern transfer method through curing by UV irradiation.
  • a master stamp that serves as a mask pattern.
  • the desired pattern is embossed from the surface on the mask.
  • the thermal process method refers to a nano-sized disc stamp contacting a substrate coated with a polymer and applying a pressure, while applying heat at a temperature above the glass transition temperature of the polymer, the polymer becomes fluid and fills a pattern between the disc stamps.
  • the original stamp is removed from the substrate, and the remaining layer in the pattern is removed by anisotropic etching to transfer the pattern.
  • the process method by UV irradiation presses a transparent disc stamp to photocurable resin, irradiates electromagnetic waves, such as an ultraviolet-ray, and hardens a photocurable resin, and then peels a disc stamp from photocurable resin,
  • the pattern formed on the stamp Is a method of transferring the resin to a resin.
  • the curable resin needs to be filled in the original stamp and irradiated with electromagnetic waves, it can be manufactured even at low pressure, and unlike the thermal process method, a large-scale manufacturing apparatus is not required.
  • the productivity is high compared to the thermal process method because it is a fast process, and since the resin or the original stamp are not expanded or contracted by heat, a high precision pattern can be formed.
  • the process method by UV irradiation is equipped with the outstanding point compared with the thermal process method.
  • the original stamp surface is treated with a release agent to reduce the adhesion between the original stamp and the resin to produce an original stamp that is difficult to adhere to the resin.
  • a release agent to reduce the adhesion between the original stamp and the resin to produce an original stamp that is difficult to adhere to the resin.
  • polypropylene siloxane polydimethylsiloxane
  • PDMS polypropylene siloxane
  • Polydimethylsiloxane is a silicone-based polymer elastomer, which can stably adhere to a relatively large area, and has a low adhesive strength with a resist surface coated with low surface energy, so that it can be easily separated from the original stamp after pattern formation.
  • Soft and weak strength makes it difficult to pattern less than 100 nm due to strain under pressure.
  • the present invention can be applied to a mold for imprint lithography to prevent expensive original stamps from being damaged by excellent release properties with the original stamps, regardless of whether the original stamps are treated with release agents. It aims at providing the photocurable resin composition which is especially excellent in chemical resistance and useful for manufacture of the mold for imprint lithography.
  • photocurable resin composition comprising:
  • R One To R 4 Each independently represent a hydrogen atom; C 2-20 Of ethylenically unsaturated groups, fluorine or C 6-20 Unsubstituted or substituted with an aromatic group 1-20 of Alkyl group or alkoxy group, where R One To R 4 At least one of C includes the ethylenically unsaturated group 1-20 of Alkyl group or alkoxy group, and R One To R 4 At least one of C contains fluorine 1-20 of An alkyl group or an alkoxy group,
  • n is an integer from 1-30,
  • R 5 to R 8 are each independently a hydrogen atom, an alkyl group of C 1-20 or an alkoxy group.
  • R 9 is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,
  • R ' is an alkyl group of C 1-6 ,
  • Q is a C 2-6 alkylene group or C 2-6 alkyleneoxy group
  • n is an integer from 0 to 4,
  • p is an integer of 0 or 1.
  • the present invention also provides a cured polymer resin to which the pattern of the original stamp is transferred by coating and curing the photocurable resin mold composition on one surface of the original stamp on which the pattern is formed, and the cured polymer resin onto which the pattern is transferred. It provides a method of manufacturing an imprint mold comprising the step of releasing from.
  • the present invention provides an imprint mold manufactured by the manufacturing method.
  • the photocurable resin mold composition according to the present invention can be applied to an imprint lithography mold to prevent expensive original stamps from being damaged by excellent release from the original stamps, regardless of whether the original stamps are treated with a release agent, or to prevent pattern formation. It is excellent in the wettability to the thermosetting or photo-curing resin for, in particular, excellent in chemical resistance and durability, it is possible to produce a fine pattern required for manufacturing various electronic devices including semiconductors, displays, etc. more quickly and stably.
  • FIG. 1 is a cross-sectional view schematically showing a method for producing a resin mold according to the present invention.
  • the photocurable silicone resin mold composition according to the present invention is characterized in that it comprises a polyaliphatic aromatic silsesquaoxane comprising an ethylenically unsaturated group and a fluorine group.
  • R One To R 4 Each independently represent a hydrogen atom; C 2-20 Of ethylenically unsaturated groups, fluorine or C 6-20 Unsubstituted or substituted with an aromatic group 1-20 of Alkyl group or alkoxy group, where R One To R 4 At least one of C includes the ethylenically unsaturated group 1-20 of Alkyl group or alkoxy group, and R One To R 4 At least one of C contains fluorine 1-20 of An alkyl group or an alkoxy group,
  • n is an integer from 1-30,
  • R 5 to R 8 are each independently a hydrogen atom, an alkyl group of C 1-20 or an alkoxy group.
  • R 9 is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,
  • R ' is an alkyl group of C 1-6 ,
  • Q is a C 2-6 alkylene group or C 2-6 alkyleneoxy group
  • n is an integer from 0 to 4,
  • p is an integer of 0 or 1.
  • the content of each component of the photocurable silicone resin mold composition may be as follows.
  • the polyaliphatic aromatic silsesquioxane containing ethylenically unsaturated groups and fluorine groups usable in the photocurable silicone resin mold composition of the present invention preferably has at least one ethylenically unsaturated group and at least one fluorine group, and has a weight average molecular weight of 1,000 It may be a compound of Ladder to cage structure of 20 to 200,000.
  • polyaliphatic aromatic silsesquioxane containing the ethylenically unsaturated group and the fluorine group may be represented by the following Formula 1:
  • R 1 to R 8 and n are as defined above.
  • the polyaliphatic aromatic silsesquioxane having the ethylenically unsaturated group and the fluorine group of the formula (1) is contained in 30 to 80 parts by weight in the silicone resin composition.
  • the amount of the silsesquioxane compound when the amount of the silsesquioxane compound is less than 30 parts by weight, the chemical resistance and releasability of the silicone resin mold composition may be lowered.
  • the amount of the silsesquioxane compound is less than 80 parts by weight, the viscosity is high, and thus, the silicone resin mold may not only be difficult to prepare but also wettability. This may fall.
  • the reactive monomer comprising at least one ethylenically unsaturated group in the molecule usable in the photocurable silicone resin mold composition of the present invention may be at least one of unsaturated carboxylic acid, unsaturated carboxylic anhydride and acrylic unsaturated compound containing at least one ethylenically unsaturated group in the molecule.
  • a reactive monomer comprising a (meth) acryl group or an epoxy group together with one or more ethylenically unsaturated groups can be used.
  • Examples of the reactive monomer containing the epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, and acrylic acid.
  • Reactive monomers containing one or more ethylenically unsaturated groups in such a molecule may be used alone or in combination of two or more thereof.
  • the reactive monomer including at least one ethylenically unsaturated group in the molecule is preferably included in the resin mold composition 5 to 50 parts by weight, more preferably 10 to 45 parts by weight.
  • the amount of the reactive monomer used is less than 5 parts by weight, the viscosity is high, there is a difficulty in the production of the resin mold, and if it exceeds 50 parts by weight, the chemical resistance and mechanical strength may be lowered.
  • the photocurable resin composition of the present invention may further include a reactive monomer including at least one fluorine group in a molecule together with a reactive monomer including at least one ethylenically unsaturated group in the molecule.
  • the reactive monomer including at least one fluorine group in the molecule may be at least one of unsaturated carboxylic acid, unsaturated carboxylic anhydride and acrylic unsaturated compound including at least one fluorine group in the molecule.
  • a reactive monomer comprising at least one fluorine group (meth) acryl group or epoxy group can be used.
  • Examples of the reactive monomer containing the fluorine group include perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropyl methacrylate and 3-perfluorohexylhydroxypropyl Methacrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, 2-perfluorohexylethyl acrylate, 3-perfluoromethylbutyl-2-hydroxypropyl acrylate, and derivatives thereof. Can be.
  • Examples of the reactive monomer containing the epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, and acrylic acid.
  • Reactive monomers containing one or more fluorine groups in the above molecules may be used alone or in combination of two or more thereof.
  • the reactive monomer containing at least one fluorine group in the molecule is preferably included in the resin mold composition 5 to 50 parts by weight, more preferably 10 to 45 parts by weight. If it is in the above range, all have good viscosity, chemical resistance and durability.
  • organic silane compound usable in the photocurable resin mold composition of the present invention an organic silane compound including a phenyl group, an amino group, a (meth) acryl group, a vinyl group or an epoxy group can be used.
  • the organosilane compound is a compound having a structure of Formula 2:
  • R 10 , m and p are as defined above.
  • the organic silane compound containing a phenyl group or an amino group has an effect of improving chemical resistance of the resin mold to improve non-swelling properties
  • the organic silane compound containing an epoxy group or a (meth) acryl group is used to cure the resin mold.
  • Increasing the density has the effect of improving the mechanical strength and hardness of the resin mold
  • the organic silane compound containing a vinyl group is effective in improving the releasability with the curable polymer resin.
  • organosilane compounds include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3- Glycidoxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane , Vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane,
  • such an organosilane compound is contained in 5 to 50 parts by weight in the resin mold composition. If the content of the organosilane compound is less than 5 parts by weight, the effect of using the organosilane compound is insignificant. If the content of the organosilane compound is more than 50 parts by weight, the viscosity decreases, making it difficult to manufacture, and there is a concern that a cracking phenomenon may occur when preparing the resin mold.
  • the photoinitiator used in the present invention may be a conventional photoinitiator that can be used in the mold composition for the conventional imprint lithography, and specific examples include Irgacure 369 (hereinafter referred to as Shiva Specialty Chemical Company), Irgacure 651, Irgacure 907, Irgacure 819, diphenyl -(2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoylformate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloromethyl-6-p-meth Oxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloro Methyl-4-methylnaphthyl-6-triazine, benzophen
  • the photoinitiator is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), and (3), and when included in the content within the above range, the resin mold produced after curing The transmittance and storage stability of can be satisfied at the same time.
  • the photocurable resin mold composition according to the present invention comprising the components of (1) to (5) as described above may further include a surfactant in order to improve applicability and to further improve releasability when removing the original mold and stripping.
  • surfactants examples include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171 (hereinafter referred to as Nippon Ink Co., Ltd.), F172, F173 FC430 (hereinafter referred to as Sumitomo Trim Corporation), FC431, KP341 (Shin-Etsu Chemical Co., Ltd.). And the like, and the content thereof is preferably contained in an amount of 0.01-2 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), (3) and (4).
  • the present invention also provides a method for producing a mold using the photocurable resin mold composition and a mold prepared by the method.
  • the method of manufacturing a mold according to the present invention comprises applying a cured photocurable resin mold composition to one surface of a disk mold on which a pattern is formed and preparing a cured polymer resin to which the pattern of the disk mold is transferred, and the cured polymer to which the pattern is transferred. Releasing the resin from the disc mold.
  • FIG. 1 is a cross-sectional view schematically showing a method for manufacturing a mold according to the present invention.
  • the pattern of the disc mold 101 to be manufactured is turned upward, and then the photocurable resin mold composition 102a according to the present invention is applied (step 1).
  • the coating process may be performed by a method commonly used in the art, for example, spin coating, slit coating, and the like, and has a thickness of 5-100 ⁇ m, preferably 5-60 ⁇ m, in the disc mold. It is preferable to apply the photocurable resin mold composition 102a as much as possible.
  • the photocurable resin mold composition 102a is cured by irradiating with nitrogen or an atmosphere in an atmosphere (step) 2).
  • the back support 103 is a transparent glass plate (bare glass), ITO (indium tin oxide) substrate, COC (cyclic olefin copolymer), PAC (polyacrylate), PC ( polycarbonate), PE (polyethylene), PEEK (polyetheretherketone), PEI (polyetherimide), PEN (polyethylenenaphthalate), PES (polyethersulfone), PET (polyethyleneterephtalate), PI (polyimide), PO (polyolefin), PMMA (polymethylmethacrylate), PSF ( polysulfone), PVA (polyvinylalcohol), PVCi (polyvinylcinnamate), TAC (triacetylcellulose), polysilicone (polysilicone), polyurethane (polyurethane), epoxy resin (epoxy Resin) and the like can be used.
  • the transmittance is 96-99.9% in the light source of 500 nm
  • a pattern transferred from the disc mold 101 is formed on one surface of the release cured polymer resin 102b.
  • the molding mold 104 is completed by aging the cured polymer resin 102b mold on which the pattern is formed (step 4).
  • aging means that the surface of the cured polymer resin mold on which the pattern is formed is excessively exposed to ultraviolet rays to improve the hardness of the mold and to completely extinguish the remaining reactors against ultraviolet rays or to extinguish the remaining reactors through heat treatment and at the same time, the surface flatness. And it means a process for further improving the adhesion with the support.
  • the aging step is preferably a process of improving the hardness of the mold by excessively exposing the surface of the mold to ultraviolet rays, may be carried out by selecting one of the exposure and the heat treatment, or both may be carried out step by step.
  • a mold having a high degree of completeness can be produced by the method according to the present invention.
  • the imprint lithography process using the mold replaces the conventional photolithography process for forming a fine pattern, thereby simplifying various steps such as exposure, development, and cleaning of the existing photolithography process, and also a manufacturing time (tact time). ), The manufacturing cost can be reduced and the productivity can be improved.
  • the stirred liquid was washed with distilled water several times to remove impurities, and then the dried liquid was vacuum-dried at room temperature for 20 hours or more to obtain a polyaliphatic aromatic silsesqui containing a desired ethylenically unsaturated group and a fluorine group having a molecular weight of 25,000 styrene.
  • Oxane 1a was prepared.
  • the stirred liquid was washed several times with distilled water to remove impurities, and then the washed liquid was vacuum-dried at room temperature for 20 hours or more to obtain a polyaliphatic aromatic silsesqui including a desired ethylenically unsaturated group and a fluorine group having a styrene equivalent molecular weight of 25,000.
  • Oxane 1b was prepared.
  • the pattern of the disc stamp 101 was faced upward, and the photocurable resin mold composition 102a prepared above was slit-coated so that its thickness became 100 ⁇ m.
  • the back support 103 is bonded onto the disc mold to which the photocurable resin mold composition is applied, and then irradiated with ultraviolet rays in a nitrogen atmosphere to cure, and the back side on which the cured polymer resin 102b to which the pattern of the disc stamp 101 is transferred is attached.
  • the support body 103 was released from the original stamp 101. Ultraviolet rays were irradiated for complete curing of the adhesive cured polymer resin 102b.
  • polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-a 15 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 15 parts by weight of dill and 15 parts by weight of (3-glycidoxypropyl) trimethoxysilane, and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator at room temperature at 300-400 rpm
  • a polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.
  • PDMS Density Polymer
  • sylgard (R) 184 silicone elastomer kit which is a material of a conventional polymer resin mold, was prepared in the same manner as in Example 1 101) was applied to a thickness of 100 ⁇ m and cured by baking in an oven at 60 ° C. for 180 minutes, and then the cured resin was released from the disc mold to prepare a polymer resin mold.
  • Light transmittance The light absorption spectrum of visible light was measured for the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4, and the light transmittance was measured and described at 400 nm.
  • Example 1 101 ⁇ ⁇ 97.5
  • Example 2 102 ⁇ ⁇ 97.7
  • Example 3 103 ⁇ ⁇ 98.7
  • Example 4 105 ⁇ ⁇ 96.3
  • Example 5 104 ⁇ ⁇ 97.0
  • Example 6 104 ⁇ ⁇ 97.1
  • Example 7 107 ⁇ ⁇ 98.8
  • Example 8 109 ⁇ ⁇ 97.4 Comparative Example 1 81 X X 95.8 Comparative Example 2 92 X ⁇ 96.3 Comparative Example 3 114 ⁇ ⁇ 97.2 Comparative Example 4 105 ⁇ X 98.4
  • the fluorine-containing silsesquioxane polymer resin molds of Examples 1 to 8 prepared using the photocurable resin mold composition of the present invention are Comparative Examples 1 to 4 Compared with, the contact angle, release property, and transmittance were found to be at the same level or higher, and in particular, the chemical resistance was excellent.
  • the photocurable resin mold composition according to the present invention can be applied to an imprint lithography mold to prevent expensive original stamps from being damaged by excellent release from the original stamps, regardless of whether the original stamps are treated with a release agent, or to prevent pattern formation. It is excellent in the wettability to the thermosetting or photo-curing resin for, in particular, excellent in chemical resistance and durability, it is possible to produce a fine pattern required for manufacturing various electronic devices including semiconductors, displays, etc. more quickly and stably.

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Abstract

The present invention relates to a light curable resin composition, and more particularly, to a light curable resin composition which can be applied to an imprint lithography mold and which exhibits superior releasability from a disk stamp regardless of whether or not the surface of the disk stamp is treated with a release agent, thus preventing the expensive disk stamp from being contaminated. More particularly, the resin composition of the present invention has excellent chemical resistance and durability, and therefore may enable micropatterns required for manufacturing various electronic devices, such as semiconductors and displays, to be produced in a quick and stable manner.

Description

광경화형 수지 조성물Photocurable resin composition

본 발명은 광경화형 수지 조성물에 관한 것으로, 보다 상세하게는 임프린트 리소그래피용 몰드에 적용되어 원판 스탬프 표면의 이형제 처리 여부와 상관없이 원판 스탬프와의 우수한 이형성으로 고가의 원판 스탬프가 오손되는 것을 막을 수 있을 뿐만 아니라, 특히 내화학성 및 내구성이 우수하여 반도체, 디스플레이 등을 포함하는 각종 전자 디바이스 제조에 필요한 미세패턴을 보다 빠르고 안정적으로 제작할 수 있는 광경화형 수지 조성물에 관한 것이다. The present invention relates to a photocurable resin composition, and more particularly, can be applied to a mold for imprint lithography to prevent expensive original stamps from being damaged due to excellent release properties with the original stamp, regardless of whether a release agent is treated on the original stamp surface. In addition, the present invention relates to a photocurable resin composition which is excellent in chemical resistance and durability, and can more quickly and stably produce fine patterns required for manufacturing various electronic devices including semiconductors and displays.

반도체, 각종 디스플레이 기기 및 광학용 시트 등을 제조할 때 기판 상에 미세 패턴을 형성하게 되는데 이때 사용되는 기술 중에 대표적인 것이 빛을 이용하는 포토리소그래피 방법이다.When manufacturing semiconductors, various display devices, optical sheets, and the like, fine patterns are formed on a substrate, and a representative photolithography method using light is a representative technique.

포토리소그래피 방법은, 반도체 웨이퍼나 유리 기판 위에 패턴 형성 대상물질을 박막으로 형성하고, 포토레지스트를 그 위에 도포한 후, 원하는 패턴이 형성된 마스크를 덮고, 포토레지스트에 빛을 조사하여 노광하고, 그 후에 현상액을 이용하여 노광된 부분 (포지티브 포토레지스트), 또는 노광되지 않은 부분 (네거티브 포토레지스트)의 포토레지스트를 제거하여 설계된 마스크 패턴의 모양대로 기판 위에 포토레지스트 패턴을 형성하고, 이후 포토레지스트 패턴이 형성된 상기 기판을 식각액에 노출하여 포토레지스트 패턴의 모양대로 초기 증착물질을 식각한 후, 스트리퍼를 이용하여 식각액에 대한 마스크 역할을 하던 포토레지스트를 최종적으로 제거함으로써 초기 증착물질의 패턴을 형성하는 방법이다. 그러나, 이러한 포토레지스트 방법은 해상도의 한계, 많은 공정과 그에 따른 긴 공정시간 및 공정에 사용되는 장비의 고가 등의 이유로 인해 제조원가가 상승하고 생산성이 저하되는 문제가 있다.In the photolithography method, a pattern forming target material is formed into a thin film on a semiconductor wafer or a glass substrate, the photoresist is applied thereon, the mask on which the desired pattern is formed is covered, the photoresist is exposed to light and then exposed. A photoresist pattern is formed on the substrate in the shape of a designed mask pattern by removing the photoresist of the exposed portion (positive photoresist) or the unexposed portion (negative photoresist) using a developer, and then the photoresist pattern is formed. After the substrate is exposed to the etchant to etch the initial deposition material in the shape of the photoresist pattern, a pattern of the initial deposition material is formed by finally removing the photoresist that used as a mask for the etching solution using a stripper. However, such a photoresist method has a problem in that manufacturing cost increases and productivity decreases due to the limitation of resolution, many processes, long process time, and expensive equipment used in the process.

최근 대규모 직접회로나 반도체, 각종 디스플레이 기기, 면역분석칩이나 DNA칩 등을 제조할 때 기판 상의 미세 패턴을 형성하게 되는데, 효율적으로 염가로 제조하는 미세 가공 방법으로서 나노 임프린트 리소그래피 방법이 주목받고 있다.Recently, when manufacturing large-scale integrated circuits, semiconductors, various display devices, immunoassay chips or DNA chips, fine patterns on a substrate are formed, and nanoimprint lithography has attracted attention as an efficient and inexpensive microfabrication method.

나노 임프린트 리소그래피는 1990년대 중반 미국 프린스턴 대학의 Chou 교수에 의해 도입된 나노 소자 제작 방법으로서, 생산성이 낮은 전자빔 리소그래피나 고가의 광학 리소그래피를 대신할 기술로 주목받고 있다.Nanoimprint lithography is a nanodevice fabrication method introduced by Professor Chou of Princeton University in the mid-1990s. It is attracting attention as a technology to replace low-productivity electron beam lithography or expensive optical lithography.

나노 임프린트 리소그래피 공정은 크게 열에 의한 공정 방법과 UV 조사에 의해 경화를 통한 패턴 전사방식으로 나눌 수 있다. 우선 나노 임프린트 리소그래피 공정을 수행하기 위해서는 마스크 패턴 역할을 하는 원판 스탬프 제작이 필요하다. 마스크 위에는 원하는 패턴이 표면으로부터 양각으로 도출되어 있다. 열에 의한 공정 방법이란 나노 사이즈의 원판 스탬프를 고분자로 코팅된 기판에 접촉시키고 압력을 가하는 동시에 고분자의 유리전이 온도 이상에 열을 가하면 고분자는 유동성을 가지게 되면서 원판 스탬프 사이를 채우면서 패턴이 형성된다. 이후 저온으로 냉각 후 원판 스탬프를 기판에서 떼어내고 패턴 내 잔류층을 이방성 에칭방법을 통해 제거함으로써 패턴을 전사시키는 방법이다. Nanoimprint lithography process can be largely divided into heat processing method and pattern transfer method through curing by UV irradiation. First, in order to perform the nanoimprint lithography process, it is necessary to manufacture a master stamp that serves as a mask pattern. The desired pattern is embossed from the surface on the mask. The thermal process method refers to a nano-sized disc stamp contacting a substrate coated with a polymer and applying a pressure, while applying heat at a temperature above the glass transition temperature of the polymer, the polymer becomes fluid and fills a pattern between the disc stamps. After cooling to low temperature, the original stamp is removed from the substrate, and the remaining layer in the pattern is removed by anisotropic etching to transfer the pattern.

이와 같이, 열에 의한 공정 방법은 고온, 고압을 가해야만 하기 때문에, 가온 기구 및 높은 프레스 압력을 공급할 수 있는 프레스 기구를 구비한 대규모 제조 장치가 필요하다는 문제점이 있다. 또한 열을 가하기 때문에 원판 스탬프와 기판의 열팽창을 고려해야 하며, 상대적으로 높은 압력을 가하기 때문에 원판 스탬프의 나노사이즈의 돌출 부분이 깨질 위험성이 높다.As described above, since the high temperature and high pressure must be applied to the heat processing method, there is a problem that a large-scale manufacturing apparatus having a heating mechanism and a press mechanism capable of supplying a high press pressure is required. In addition, the thermal expansion of the original stamp and the substrate should be considered because of the application of heat, and because of the relatively high pressure, there is a high risk of breaking the nano-sized protrusions of the original stamp.

한편, UV 조사에 의한 공정 방법은 투명 원판 스탬프를 광 경화성 수지에 압박하고, 자외선 등의 전자파를 조사하여 광 경화성 수지를 경화시킨 후, 원판 스탬프를 광 경화성 수지로부터 박리함으로써, 스탬프 상에 형성된 패턴을 수지에 전사시키는 방법이다.On the other hand, the process method by UV irradiation presses a transparent disc stamp to photocurable resin, irradiates electromagnetic waves, such as an ultraviolet-ray, and hardens a photocurable resin, and then peels a disc stamp from photocurable resin, The pattern formed on the stamp Is a method of transferring the resin to a resin.

이러한, UV 조사에 의한 공정 방법에서는 원판 스탬프 내에 경화성 수지를 충전하고, 전자파를 조사할 수 있으면 되기 때문에, 낮은 압력에서도 제조가 가능하며 열 공정 방법과는 달리 대규모 제조 장치를 필요로 하지 않는다. 또한, 상온에서 수행되며, 경화시간이 짧기 때문에 빠른 공정으로 열 공정 방법과는 비교하면 생산성이 높으며 열에 의해서 수지나 원판 스탬프가 팽창, 수축되는 경우가 없기 때문에 고정밀도의 패턴을 형성시킬 수 있다. 이와 같이, UV 조사에 의한 공정 방법은 열 공정 방법에 비하여 우수한 점을 구비하고 있다.In such a process by UV irradiation, since the curable resin needs to be filled in the original stamp and irradiated with electromagnetic waves, it can be manufactured even at low pressure, and unlike the thermal process method, a large-scale manufacturing apparatus is not required. In addition, since it is performed at room temperature and the curing time is short, the productivity is high compared to the thermal process method because it is a fast process, and since the resin or the original stamp are not expanded or contracted by heat, a high precision pattern can be formed. Thus, the process method by UV irradiation is equipped with the outstanding point compared with the thermal process method.

단지, UV 조사 공정 방법에서도 원판 스탬프와 경화된 수지를 박리시킬 때에 원판 스탬프와 경화된 수지와의 압착이나 마찰이 원인이 되어, 부분적으로 수지가 원판 스탬프와 함께 박리되어 고가의 원판 스탬프의 홈을 폐색시키는 경우가 있다.However, even in the UV irradiation process method, when the original stamp and the cured resin are peeled off, compression or friction between the original stamp and the cured resin may be caused, and the resin partially peels together with the original stamp, thereby forming grooves of the expensive original stamp. It may be blocked.

그 때문에, UV 조사 공정 방법에 있어서도, 패턴의 전사를 반복하는 중에 몰드의 홈이 폐색되어, 고가의 원판 스탬프가 오손됨과 동시에, 전사된 패턴의 일부에 결손이 생겨 버린다는 문제점이 있다.Therefore, also in the UV irradiation process method, there exists a problem that the groove | channel of a mold is clogged while repeating transfer of a pattern, an expensive original stamp is damaged, and a defect arises in a part of transferred pattern.

이 문제점을 해결하기 위해서, 원판 스탬프 표면을 이형제로 처리하여 원판 스탬프와 수지의 부착력을 감소시켜 수지와 부착되기 어려운 원판 스탬프를 제조하는 것이 시도되고 있다. 그러나 이형제의 내구성 감소로 인하여 패턴을 전사할 때마다 이형제 처리하는 경우에는 생산성이 저하된다는 문제점이 있다.In order to solve this problem, the original stamp surface is treated with a release agent to reduce the adhesion between the original stamp and the resin to produce an original stamp that is difficult to adhere to the resin. However, when the release agent treatment is performed every time the pattern is transferred due to the reduced durability of the release agent, there is a problem that productivity is lowered.

기존의 수지몰드에 사용된 대표적인 것으로는 제조 가격이 저렴하면서 소수성의 이형 성질을 나타내는 것으로 폴리디메틸실록산(polydimethylsiloxane, PDMS)이 가장 많이 사용되고 있다. 폴리디메틸실록산은 실리콘계 고분자 탄성체로써 상대적으로 넓은 영역에 안정적으로 점착할 수 있을 수 있으며 낮은 표면에너지로 도포된 레지스트 표면과의 접착력이 작아 패턴형성 후 원판 스탬프로부터 쉽게 분리가 가능하다는 장점이 있는 반면에 유연하고 강도가 약해서 가해지는 압력에 의한 변형 때문에 100nm 이하의 패턴이 어렵다. 또한 낮은 기계적 강도로 변형이 쉽게 일어나고, 낮은 내화학성에 의해 일반적인 유기용매에 팽윤(swelling)되어 변형이 된다는 문제가 있다.Representatives used in the existing resin molds are polypropylene siloxane (polydimethylsiloxane, PDMS) is the most used to show the hydrophobic release properties and low manufacturing cost. Polydimethylsiloxane is a silicone-based polymer elastomer, which can stably adhere to a relatively large area, and has a low adhesive strength with a resist surface coated with low surface energy, so that it can be easily separated from the original stamp after pattern formation. Soft and weak strength makes it difficult to pattern less than 100 nm due to strain under pressure. In addition, there is a problem that deformation occurs easily due to low mechanical strength, and swelling in a general organic solvent due to low chemical resistance causes deformation.

상기와 같은 문제점을 해결하기 위해, 본 발명은 임프린트 리소그래피용 몰드에 적용되어 원판 스탬프 표면의 이형제 처리 여부와 상관없이 원판 스탬프와의 우수한 이형성으로 고가의 원판 스탬프가 오손되는 것을 막을 수 있을 뿐만 아니라, 특히 내화학성이 우수하여 임프린트 리소그래피용 몰드의 제조에 유용한 광경화형 수지 조성물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention can be applied to a mold for imprint lithography to prevent expensive original stamps from being damaged by excellent release properties with the original stamps, regardless of whether the original stamps are treated with release agents. It aims at providing the photocurable resin composition which is especially excellent in chemical resistance and useful for manufacture of the mold for imprint lithography.

본 발명은 또한, 반도체, 디스플레이 등을 포함한 각종 전자 디바이스 산업 공정에 필요한 미세패턴을 안정적이고 용이하게 형성할 수 있는 임프린트 몰드의 제조방법 및 상기 방법에 의해 제조된 임프린트 몰드를 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a method for producing an imprint mold which can stably and easily form fine patterns required for various electronic device industrial processes including semiconductors, displays, and the like and an imprint mold manufactured by the above method. .

상기 목적을 달성하기 위해 본 발명은,The present invention to achieve the above object,

(1) 하기 화학식 1의 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산;(1) a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group represented by the following Formula 1;

(2) 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머;(2) reactive monomers comprising at least one unsaturated group in the molecule;

(3) 하기 화학식 2의 유기실란계 화합물 및(3) an organosilane compound of Formula 2 and

(4) 광개시제(4) photoinitiator

를 포함하는 것을 특징으로 하는 광경화형 수지 조성물을 제공한다:It provides a photocurable resin composition comprising:

[화학식 1][Formula 1]

Figure PCTKR2012005657-appb-I000001
Figure PCTKR2012005657-appb-I000001

상기 식에서,Where

R1 내지 R4는 각각 독립적으로 수소원자; C2-20의 에틸렌성 불포화기, 불소 또는 C6-20의 방향족기로 치환되거나 치환되지 않은 C1-20의 알킬기 또는 알콕시기를 나타내고, 이때 R1 내지 R4 중 적어도 하나 이상은 상기 에틸렌성의 불포화기를 포함하는 C1-20의 알킬기 또는 알콕시기이고, 또한 R1 내지 R4 중 적어도 하나 이상은 불소를 포함하는 C1-20의 알킬기 또는 알콕시기이고,ROne To R4Each independently represent a hydrogen atom; C2-20Of ethylenically unsaturated groups, fluorine or C6-20Unsubstituted or substituted with an aromatic group1-20of Alkyl group or alkoxy group, where ROne To R4At least one of C includes the ethylenically unsaturated group1-20of Alkyl group or alkoxy group, and ROne To R4At least one of C contains fluorine1-20of An alkyl group or an alkoxy group,

n은 1-30의 정수이며,n is an integer from 1-30,

R5 내지 R8은 각각 독립적으로 수소원자, C1-20의 알킬기 또는 알콕시기이다.R 5 to R 8 are each independently a hydrogen atom, an alkyl group of C 1-20 or an alkoxy group.

[화학식 2][Formula 2]

R9 4-m-Qp-Si-(OR10)m R 9 4-m -Q p -Si- (OR 10 ) m

상기 식에서,Where

R9는 페닐기, 아미노기, (메타)아크릴기, 비닐기, 에폭시기 및 이들의 조합으로 이루어진 군에서 선택되고,R 9 is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,

R10은 C1-5의 알킬기, C3-10의 시클로알킬기, C6-12의 아릴기, -OCR', -CR'=N-OH 및 이들의 조합으로 이루어진 군에서 선택되며,R 10 is selected from the group consisting of an alkyl group of C 1-5 , a cycloalkyl group of C 3-10 , an aryl group of C 6-12 , -OCR ', -CR' = N-OH, and a combination thereof,

이때 R'은 C1-6의 알킬기이고,Wherein R 'is an alkyl group of C 1-6 ,

Q는 C2-6의 알킬렌기 또는 C2-6 알킬렌옥시기이고,Q is a C 2-6 alkylene group or C 2-6 alkyleneoxy group,

m은 0 내지 4의 정수이며,m is an integer from 0 to 4,

p는 0 또는 1의 정수이다.p is an integer of 0 or 1.

본 발명은 또한, 패턴이 형성된 원판 스탬프 일면에 상기 광경화형 수지 몰드 조성물을 도포하고 경화시켜 원판 스탬프의 패턴이 전사된 경화 고분자 수지를 제조하는 단계, 및 상기 패턴이 전사된 경화 고분자 수지를 원판 스탬프로부터 이형시키는 단계를 포함하는 임프린트 몰드의 제조방법을 제공한다.The present invention also provides a cured polymer resin to which the pattern of the original stamp is transferred by coating and curing the photocurable resin mold composition on one surface of the original stamp on which the pattern is formed, and the cured polymer resin onto which the pattern is transferred. It provides a method of manufacturing an imprint mold comprising the step of releasing from.

또한, 본 발명은 상기 제조방법에 의하여 제조된 임프린트 몰드를 제공한다.In addition, the present invention provides an imprint mold manufactured by the manufacturing method.

본 발명에 따른 광경화형 수지 몰드 조성물은 임프린트 리소그래피 몰드에 적용되어 원판 스탬프 표면의 이형제 처리 여부와 상관없이 원판 스탬프와의 우수한 이형성으로 고가의 원판 스탬프가 오손되는 것을 막을 수 있을 뿐만 아니라, 패턴형성을 위한 열경화 또는 광경화 수지에 대해 젖음성이 우수하며, 특히 내화학성 및 내구성이 우수하여 반도체, 디스플레이 등을 포함하는 각종 전자 디바이스 제조에 필요한 미세패턴을 보다 빠르고 안정적으로 제작할 수 있다.The photocurable resin mold composition according to the present invention can be applied to an imprint lithography mold to prevent expensive original stamps from being damaged by excellent release from the original stamps, regardless of whether the original stamps are treated with a release agent, or to prevent pattern formation. It is excellent in the wettability to the thermosetting or photo-curing resin for, in particular, excellent in chemical resistance and durability, it is possible to produce a fine pattern required for manufacturing various electronic devices including semiconductors, displays, etc. more quickly and stably.

도 1은 본 발명에 따른 수지 몰드의 제조방법을 개략적으로 도시하는 단면도이다.1 is a cross-sectional view schematically showing a method for producing a resin mold according to the present invention.

본 발명에 따른 광경화형 실리콘 수지 몰드 조성물은 에틸렌성 불포화기 및 불소기를 포함하는 폴리지방족방향족 실세스퀘옥산을 포함하는 것을 특징으로 한다.The photocurable silicone resin mold composition according to the present invention is characterized in that it comprises a polyaliphatic aromatic silsesquaoxane comprising an ethylenically unsaturated group and a fluorine group.

즉, 본 발명에 따른 광경화형 실리콘 수지 몰드 조성물은,That is, the photocurable silicone resin mold composition according to the present invention,

(1) 하기 화학식 1의 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산;(1) a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group represented by the following Formula 1;

(2) 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머;(2) reactive monomers comprising at least one unsaturated group in the molecule;

(3) 하기 화학식 2의 유기실란계 화합물 및(3) an organosilane compound of Formula 2 and

(4) 광개시제(4) photoinitiator

를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.

[화학식 1][Formula 1]

Figure PCTKR2012005657-appb-I000002
Figure PCTKR2012005657-appb-I000002

상기 식에서,Where

R1 내지 R4는 각각 독립적으로 수소원자; C2-20의 에틸렌성 불포화기, 불소 또는 C6-20의 방향족기로 치환되거나 치환되지 않은 C1-20의 알킬기 또는 알콕시기를 나타내고, 이때 R1 내지 R4 중 적어도 하나 이상은 상기 에틸렌성의 불포화기를 포함하는 C1-20의 알킬기 또는 알콕시기이고, 또한 R1 내지 R4 중 적어도 하나 이상은 불소를 포함하는 C1-20의 알킬기 또는 알콕시기이고,ROne To R4Each independently represent a hydrogen atom; C2-20Of ethylenically unsaturated groups, fluorine or C6-20Unsubstituted or substituted with an aromatic group1-20of Alkyl group or alkoxy group, where ROne To R4At least one of C includes the ethylenically unsaturated group1-20of Alkyl group or alkoxy group, and ROne To R4At least one of C contains fluorine1-20of An alkyl group or an alkoxy group,

n은 1-30의 정수이며,n is an integer from 1-30,

R5 내지 R8은 각각 독립적으로 수소원자, C1-20의 알킬기 또는 알콕시기이다.R 5 to R 8 are each independently a hydrogen atom, an alkyl group of C 1-20 or an alkoxy group.

[화학식 2][Formula 2]

R9 4-m-Qp-Si-(OR10)m R 9 4-m -Q p -Si- (OR 10 ) m

상기 식에서,Where

R9는 페닐기, 아미노기, (메타)아크릴기, 비닐기, 에폭시기 및 이들의 조합으로 이루어진 군에서 선택되고,R 9 is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,

R10은 C1-5의 알킬기, C3-10의 시클로알킬기, C6-12의 아릴기, -OCR', -CR'=N-OH 및 이들의 조합으로 이루어진 군에서 선택되며,R 10 is selected from the group consisting of an alkyl group of C 1-5 , a cycloalkyl group of C 3-10 , an aryl group of C 6-12 , -OCR ', -CR' = N-OH, and a combination thereof,

이때 R'은 C1-6의 알킬기이고,Wherein R 'is an alkyl group of C 1-6 ,

Q는 C2-6의 알킬렌기 또는 C2-6 알킬렌옥시기이고,Q is a C 2-6 alkylene group or C 2-6 alkyleneoxy group,

m은 0 내지 4의 정수이며,m is an integer from 0 to 4,

p는 0 또는 1의 정수이다.p is an integer of 0 or 1.

바람직하기로 상기 광경화형 실리콘 수지 몰드 조성물의 각 성분의 함량은 하기와 같은 것이 좋다.Preferably, the content of each component of the photocurable silicone resin mold composition may be as follows.

(1) 상기 화학식 1의 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산 30 내지 80 중량부;(1) 30 to 80 parts by weight of polyaliphatic aromatic silsesquioxane containing ethylenically unsaturated group and fluorine group of Formula 1;

(2) 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머 5 내지 50 중량부;;(2) 5 to 50 parts by weight of a reactive monomer comprising at least one unsaturated group in the molecule;

(3) 하기 화학식 2의 유기실란계 화합물 5 내지 50 중량부; 및(3) 5 to 50 parts by weight of the organosilane compound of Formula 2; And

(4) 상기 (1), (2), 및 (3)성분의 총 합계량 100 중량부에 대하여 광개시제 0.1 내지 10 중량부.(4) 0.1-10 weight part of photoinitiators with respect to 100 weight part of total amounts of said (1), (2), and (3) component.

이하 각 성분들에 대하여 설명한다.Each component is demonstrated below.

(1) 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1) polyaliphatic aromatic silsesquioxanes containing ethylenically unsaturated groups and fluorine groups

본 발명의 광경화형 실리콘 수지 몰드 조성물에 사용가능한 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산은 분자 내에 하나 이상의 에틸렌성 불포화기, 하나 이상의 불소기를 가지는 것이 바람직하며, 중량평균분자량 1,000 내지 200,000의 래더 (Ladder) 내지 케이지 (Cage) 구조의 화합물일 수 있다.The polyaliphatic aromatic silsesquioxane containing ethylenically unsaturated groups and fluorine groups usable in the photocurable silicone resin mold composition of the present invention preferably has at least one ethylenically unsaturated group and at least one fluorine group, and has a weight average molecular weight of 1,000 It may be a compound of Ladder to cage structure of 20 to 200,000.

상기 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산은 하기 화학식 1로 표시될 수 있다:The polyaliphatic aromatic silsesquioxane containing the ethylenically unsaturated group and the fluorine group may be represented by the following Formula 1:

[화학식 1][Formula 1]

Figure PCTKR2012005657-appb-I000003
Figure PCTKR2012005657-appb-I000003

상기 식에서, 상기 식에서, R1 내지 R8 및 n은 상기에서 정의한 바와 같다.Wherein, R 1 to R 8 and n are as defined above.

상기 화학식 1의 에틸렌성 불포화기와 불소기를 가지는 폴리지방족방향족 실세스퀴옥산은 실리콘 수지 조성물 중에 30 내지 80 중량부로 포함되는 것이 바람직하다.It is preferable that the polyaliphatic aromatic silsesquioxane having the ethylenically unsaturated group and the fluorine group of the formula (1) is contained in 30 to 80 parts by weight in the silicone resin composition.

이때, 실세스퀴옥산 화합물의 사용량이 30 중량부 미만이면 실리콘 수지 몰드 조성물의 내화학성 및 이형성이 저하될 우려가 있고, 80 중량부를 초과하면 점도가 높아져 실리콘 수지몰드 제작에 어려움이 있을 뿐만 아니라 젖음성이 저하될 우려가 있다.In this case, when the amount of the silsesquioxane compound is less than 30 parts by weight, the chemical resistance and releasability of the silicone resin mold composition may be lowered. When the amount of the silsesquioxane compound is less than 80 parts by weight, the viscosity is high, and thus, the silicone resin mold may not only be difficult to prepare but also wettability. This may fall.

(2) 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 반응성 모노머(2) reactive monomers comprising at least one ethylenically unsaturated group in the molecule

본 발명의 광경화형 실리콘 수지 몰드 조성물에 사용가능한 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 반응성 모노머는 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 불포화 카르본산, 불포화 카르본산 무수물 및 아크릴계 불포화 화합물 중 하나 이상일 수 있다. 바람직하게는 하나 이상의 에틸렌성 불포화기와 함께 (메타)아크릴기, 또는 에폭시기를 포함하는 반응성 모노머를 사용할 수 있다.The reactive monomer comprising at least one ethylenically unsaturated group in the molecule usable in the photocurable silicone resin mold composition of the present invention may be at least one of unsaturated carboxylic acid, unsaturated carboxylic anhydride and acrylic unsaturated compound containing at least one ethylenically unsaturated group in the molecule. Can be. Preferably, a reactive monomer comprising a (meth) acryl group or an epoxy group together with one or more ethylenically unsaturated groups can be used.

상기 (메타)아크릴기를 포함하는 반응성 모노머로는, 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 시클로헥실 메타크릴레이트, 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트, 1,6-헥산디올디아크릴레이트 등을 들 수 있다.As a reactive monomer containing the said (meth) acryl group, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert- butyl methacrylate, methyl acrylate, isopropyl Acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-Adaman Methyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate , Isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate Y, 1, 6- hexanediol diacrylate, etc. are mentioned.

상기 에폭시기를 포함하는 반응성 모노머로는 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, 아크릴산-3,4-에폭시 시클로헥실메틸, 메타크릴산-3,4-에폭시 시클로헥실메틸, 4-비닐시클로헥센옥사이드, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, p-비닐벤질글리시딜에테르 등을 들 수 있다.Examples of the reactive monomer containing the epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacryl Acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxy cyclohexyl Methyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Can be mentioned.

상기와 같은 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 반응성 모노머는 1종 단독으로 사용될 수도 있고, 2종 이상 혼합하여 사용될 수도 있다.Reactive monomers containing one or more ethylenically unsaturated groups in such a molecule may be used alone or in combination of two or more thereof.

본 발명에서 상기 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 반응성 모노머는 수지 몰드 조성물 중에 5 내지 50 중량부로 포함되는 것이 바람직하고, 더욱 바람직하게는 10 내지 45 중량부로 포함되는 것이 좋다.In the present invention, the reactive monomer including at least one ethylenically unsaturated group in the molecule is preferably included in the resin mold composition 5 to 50 parts by weight, more preferably 10 to 45 parts by weight.

이때, 상기 반응성 모노머의 사용량이 5 중량부 미만이면 점도가 높아져 수지 몰드 제작에 어려움이 있으며, 50 중량부를 초과하면 내화학성, 기계적 강도가 저하될 우려가 있다.At this time, if the amount of the reactive monomer used is less than 5 parts by weight, the viscosity is high, there is a difficulty in the production of the resin mold, and if it exceeds 50 parts by weight, the chemical resistance and mechanical strength may be lowered.

바람직하기로 본 발명의 광경화성 수지 조성물은 상기 분자 내에 하나 이상의 에틸렌성 불포화기를 포함하는 반응성 모노머와 함께 분자 내에 하나 이상의 불소기를 포함하는 반응성 모노머를 더욱 포함하는 것이 좋다.Preferably, the photocurable resin composition of the present invention may further include a reactive monomer including at least one fluorine group in a molecule together with a reactive monomer including at least one ethylenically unsaturated group in the molecule.

상기 분자 내에 하나 이상의 불소기를 포함하는 반응성 모노머는 분자 내에 하나 이상의 불소기를 포함하는 불포화 카르본산, 불포화 카르본산 무수물 및 아크릴계 불포화 화합물 중 하나 이상일 수 있다. 바람직하게는 하나 이상의 불소기와 (메타)아크릴기, 또는 에폭시기를 포함하는 반응성 모노머를 사용할 수 있다.The reactive monomer including at least one fluorine group in the molecule may be at least one of unsaturated carboxylic acid, unsaturated carboxylic anhydride and acrylic unsaturated compound including at least one fluorine group in the molecule. Preferably, a reactive monomer comprising at least one fluorine group (meth) acryl group or epoxy group can be used.

상기 불소기를 포함하는 반응성 모노머로는, 퍼플루오로헥실에틸렌, 1,4-디비닐도데카플루오로헥산, 3-퍼플루오로부틸하이드록시프로필메타크릴레이트, 3-퍼플루오로헥실하이드록실프로필메타크릴레이트, 트리플루오로에틸메타크릴레이트, 테트라플루오로프로필메타크릴레이트, 2-퍼플루오로헥실에틸아크릴레이트, 3-퍼플루오로메틸부틸-2-하이드록시프로필아크릴레이트 등과 그 유도체를 들 수 있다. Examples of the reactive monomer containing the fluorine group include perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropyl methacrylate and 3-perfluorohexylhydroxypropyl Methacrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, 2-perfluorohexylethyl acrylate, 3-perfluoromethylbutyl-2-hydroxypropyl acrylate, and derivatives thereof. Can be.

상기 (메타)아크릴기를 포함하는 반응성 모노머로는, 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 시클로헥실 메타크릴레이트, 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트, 1,6-헥산디올디아크릴레이트 등을 들 수 있다.As a reactive monomer containing the said (meth) acryl group, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert- butyl methacrylate, methyl acrylate, isopropyl Acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-Adaman Methyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate , Isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate Y, 1, 6- hexanediol diacrylate, etc. are mentioned.

상기 에폭시기를 포함하는 반응성 모노머로는 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, 아크릴산-3,4-에폭시 시클로헥실메틸, 메타크릴산-3,4-에폭시 시클로헥실메틸, 4-비닐시클로헥센옥사이드, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, p-비닐벤질글리시딜에테르 등을 들 수 있다.Examples of the reactive monomer containing the epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacryl Acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxy cyclohexyl Methyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Can be mentioned.

상기와 같은 분자 내에 하나 이상의 불소기를 포함하는 반응성 모노머는 1종 단독으로 사용될 수도 있고, 2종 이상 혼합하여 사용될 수도 있다.Reactive monomers containing one or more fluorine groups in the above molecules may be used alone or in combination of two or more thereof.

본 발명에서 상기 분자 내에 하나 이상의 불소기를 포함하는 반응성 모노머는 수지 몰드 조성물 중에 5 내지 50 중량부로 포함되는 것이 바람직하고, 더욱 바람직하게는 10 내지 45 중량부로 포함되는 것이 좋다. 상기 범위 내인 경우 점도, 내화학성 및 내구성이 모두 좋다.In the present invention, the reactive monomer containing at least one fluorine group in the molecule is preferably included in the resin mold composition 5 to 50 parts by weight, more preferably 10 to 45 parts by weight. If it is in the above range, all have good viscosity, chemical resistance and durability.

(3) 유기 실란계 화합물(3) organosilane compound

본 발명의 광경화형 수지 몰드 조성물에 사용가능한 유기 실란계 화합물로는 페닐기, 아미노기, (메타)아크릴기, 비닐기 또는 에폭시기를 포함하는 유기 실란계 화합물을 사용할 수 있다.As the organic silane compound usable in the photocurable resin mold composition of the present invention, an organic silane compound including a phenyl group, an amino group, a (meth) acryl group, a vinyl group or an epoxy group can be used.

구체적으로는 상기 유기 실란계 화합물은 하기 화학식 2의 구조를 갖는 화합물이다:Specifically, the organosilane compound is a compound having a structure of Formula 2:

[화학식 2][Formula 2]

R9 4-m-Qp-Si-(OR10)m R 9 4-m -Q p -Si- (OR 10 ) m

상기 식에서, R9. R10, m 및 p는 상기에서 정의한 바와 같다.Wherein R 9 . R 10 , m and p are as defined above.

상기 유기 실란계 화합물 중에서도 페닐기 또는 아미노기를 포함하는 유기 실란 화합물은 수지 몰드의 내화학성을 증가시켜 비팽윤성을 향상시키는 효과가 있고, 에폭시기 또는 (메타)아크릴기를 포함하는 유기 실란 화합물은 수지 몰드의 경화 밀도를 증가시켜 수지 몰드의 기계적 강도 및 경도를 향상시키는 효과가 있으며, 또한 비닐기를 포함하는 유기 실란계 화합물은 경화성 고분자 수지와의 이형성 향상에 효과가 있다.Among the organic silane compounds, the organic silane compound containing a phenyl group or an amino group has an effect of improving chemical resistance of the resin mold to improve non-swelling properties, and the organic silane compound containing an epoxy group or a (meth) acryl group is used to cure the resin mold. Increasing the density has the effect of improving the mechanical strength and hardness of the resin mold, and the organic silane compound containing a vinyl group is effective in improving the releasability with the curable polymer resin.

유기 실란계 화합물의 구체적인 예로는 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3-(메타아크릴옥시)프로필트리메톡시실란, 3,4-에폭시부틸트리메톡시실란, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 아미노프로필트리에톡시실란, 비닐트리에톡시실란, 비닐트리-t-부톡시실란, 비닐트리이소부톡시실란, 비닐트리이소프로폭시실란, 비닐트리페녹시실란, 페닐트리에톡시실란, 페닐트리메톡시실란, 아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 병용하여 사용할 수도 있다. 최종 제조되는 수지 몰드 조성물의 물성 개량면에서는 2종 이상을 혼합하여 사용하는 것이 보다 바람직하다.Specific examples of the organosilane compounds include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3- Glycidoxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane , Vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silanes; and the like, and may be used alone or in combination of two or more of them. The. It is more preferable to mix and use 2 or more types from the viewpoint of the physical property improvement of the resin mold composition finally manufactured.

상기와 같은 유기 실란계 화합물은 수지 몰드 조성물 중에 5 내지 50 중량부로 포함되는 것이 바람직하다. 유기 실란계 화합물의 함량이 5 중량부 미만이면 유기 실란 화합물 사용에 따른 효과가 미미하고, 50 중량부를 초과하면 점도가 저하되어 제작에 어려움이 있고, 수지 몰드 제작시 갈라짐 현상이 발생할 우려가 있다.It is preferable that such an organosilane compound is contained in 5 to 50 parts by weight in the resin mold composition. If the content of the organosilane compound is less than 5 parts by weight, the effect of using the organosilane compound is insignificant. If the content of the organosilane compound is more than 50 parts by weight, the viscosity decreases, making it difficult to manufacture, and there is a concern that a cracking phenomenon may occur when preparing the resin mold.

(4) 광개시제(4) photoinitiator

본 발명에 사용되는 광개시제는 통상적으로 임프린트 리소그래피용 몰드 조성물에 사용될 수 있는 통상의 광개시제가 사용가능하며, 구체적인 예로 Irgacure 369 (이하, 시바스페셜티케미컬사제), Irgacure 651, Irgacure 907, Irgacure 819, 다이페닐-(2,4,6-트리메틸벤조일)포스핀옥사이드, 메틸벤조일포르메이트, 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트, 2,4-비스트리클로로메틸-6-p-메톡시스티릴-s-트리아진, 2-p-메톡시스티릴-4,6-비스트리클로로메틸-s-트리아진, 2,4-트리클로로메틸-6-트리아진, 2,4-트리클로로메틸-4-메틸나프틸-6-트리아진, 벤조페논, p-(다이에틸아미노)벤조페논, 2,2-다이클로로-4-페녹시아세토페논, 2,2-다이에톡시아세토페논, 2-도데실티오크산톤, 2,4-다이메틸티오크산톤, 2,4-다이에틸티오크산톤, 또는 2,2-비스(2-클로로페닐)-4,4,5,5-테트라페닐-1,2-비이미다졸 등을 사용할 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 병용하여 사용할 수 있다.The photoinitiator used in the present invention may be a conventional photoinitiator that can be used in the mold composition for the conventional imprint lithography, and specific examples include Irgacure 369 (hereinafter referred to as Shiva Specialty Chemical Company), Irgacure 651, Irgacure 907, Irgacure 819, diphenyl -(2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoylformate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloromethyl-6-p-meth Oxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloro Methyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxycetophenone, 2,2-diethoxyacetophenone , 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, or 2,2-bis (2-chlorophenyl) -4,4,5,5-tetra Phenyl-1,2- ratio Imidazole etc. can be used and can be used individually by 1 type or in combination of 2 or more types.

상기 광개시제는 상기 성분 (1), (2), 및 (3)의 총 합계량 100 중량부에 대하여 0.1-10 중량부로 포함되는 것이 바람직하며, 상기 범위 내의 함량으로 포함될 때, 경화 후 제작된 수지 몰드의 투과도 및 보존안정성을 동시에 만족시킬 수 있다.The photoinitiator is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), and (3), and when included in the content within the above range, the resin mold produced after curing The transmittance and storage stability of can be satisfied at the same time.

상기와 같은 (1) 내지 (5)의 성분으로 이루어지는 본 발명에 따른 광경화형 수지 몰드 조성물은, 도포성을 향상시키고 원판몰드와 탈거시 이형성을 더욱 좋게 하기 위해 계면활성제를 더 포함할 수 있다.The photocurable resin mold composition according to the present invention comprising the components of (1) to (5) as described above may further include a surfactant in order to improve applicability and to further improve releasability when removing the original mold and stripping.

상기 계면활성제로는 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르, F171 (이하, 대일본잉크사제), F172, F173 FC430 (이하, 쓰미또모트리엠사), FC431, KP341 (신에쓰가가쿠고쿄사제) 등을 들 수 있으며, 그 함량은 상기 성분 (1), (2), (3) 및 (4)의 총 합계량 100 중량부에 대하여 0.01-2 중량부로 포함되는 것이 바람직하다.Examples of the surfactants include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171 (hereinafter referred to as Nippon Ink Co., Ltd.), F172, F173 FC430 (hereinafter referred to as Sumitomo Trim Corporation), FC431, KP341 (Shin-Etsu Chemical Co., Ltd.). And the like, and the content thereof is preferably contained in an amount of 0.01-2 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), (3) and (4).

또한 본 발명은 상기의 광경화형 수지 몰드 조성물을 이용한 몰드의 제조방법 및 상기 방법에 의하여 제조된 몰드를 제공한다.The present invention also provides a method for producing a mold using the photocurable resin mold composition and a mold prepared by the method.

본 발명에 따른 몰드의 제조방법은 패턴이 형성된 원판 몰드 일면에 상기 광경화형 수지 몰드 조성물을 도포하고 경화시켜 원판 몰드의 패턴이 전사된 경화 고분자 수지를 제조하는 단계, 및 상기 패턴이 전사된 경화 고분자 수지를 원판 몰드로부터 이형시키는 단계를 포함한다.The method of manufacturing a mold according to the present invention comprises applying a cured photocurable resin mold composition to one surface of a disk mold on which a pattern is formed and preparing a cured polymer resin to which the pattern of the disk mold is transferred, and the cured polymer to which the pattern is transferred. Releasing the resin from the disc mold.

이하 첨부된 도 1을 참조하여 본 발명에 따른 몰드의 제조방법을 상세히 설명한다.Hereinafter, a method of manufacturing a mold according to the present invention will be described in detail with reference to FIG. 1.

도 1은 본 발명에 따른 몰드의 제조방법을 개략적으로 도시하는 단면도이다.1 is a cross-sectional view schematically showing a method for manufacturing a mold according to the present invention.

도 1을 참조하면, 먼저 제조하고자 하는 원판 몰드 (101)의 패턴이 위로 향하도록 한 다음 본 발명에 따른 광경화형 수지 몰드 조성물 (102a)을 도포한다 (단계 1).Referring to FIG. 1, first, the pattern of the disc mold 101 to be manufactured is turned upward, and then the photocurable resin mold composition 102a according to the present invention is applied (step 1).

이때, 상기 도포 공정은 당분야에서 통상적으로 사용하는 방법, 예를 들어 스핀코팅, 슬릿 코팅 등의 방법으로 수행할 수 있으며, 원판 몰드에 5-100 ㎛, 바람직하게는 5-60 ㎛의 두께가 되도록 광경화형 수지 몰드 조성물 (102a)을 도포하는 것이 바람직하다.In this case, the coating process may be performed by a method commonly used in the art, for example, spin coating, slit coating, and the like, and has a thickness of 5-100 μm, preferably 5-60 μm, in the disc mold. It is preferable to apply the photocurable resin mold composition 102a as much as possible.

상기 원판 몰드 (101)에 도포된 광경화형 수지 몰드 조성물 (102a) 위에 배면 지지체 (103)를 합착시킨 후, 질소 또는 대기 중 분위기에서 광조사하여 광경화형 수지 몰드 조성물 (102a)을 경화시킨다 (단계 2).After bonding the back support 103 onto the photocurable resin mold composition 102a applied to the disc mold 101, the photocurable resin mold composition 102a is cured by irradiating with nitrogen or an atmosphere in an atmosphere (step) 2).

이때, 상기 배면 지지체 (103)로는 500 ㎚ 파장의 광원에서 투과율이 적어도 85 % 이상인 투명 유리판 (bare glass), ITO (indium tin oxide) 기판, COC (cyclic olefin copolymer), PAc (polyacrylate), PC (polycarbonate), PE (polyethylene), PEEK (polyetheretherketone), PEI (polyetherimide), PEN (polyethylenenaphthalate), PES (polyethersulfone), PET (polyethyleneterephtalate), PI (polyimide), PO (polyolefin), PMMA (polymethylmethacrylate), PSF (polysulfone), PVA (polyvinylalcohol), PVCi (polyvinylcinnamate), TAC (triacetylcellulose), 폴리실리콘 (polysilicone), 폴리우레탄 (polyurethane), 에폭시 수지 (epoxy Resin) 등을 사용할 수 있다. 바람직하게는 상기 500 ㎚ 파장의 광원에서 투과율이 96-99.9 %인 것이 좋다.In this case, the back support 103 is a transparent glass plate (bare glass), ITO (indium tin oxide) substrate, COC (cyclic olefin copolymer), PAC (polyacrylate), PC ( polycarbonate), PE (polyethylene), PEEK (polyetheretherketone), PEI (polyetherimide), PEN (polyethylenenaphthalate), PES (polyethersulfone), PET (polyethyleneterephtalate), PI (polyimide), PO (polyolefin), PMMA (polymethylmethacrylate), PSF ( polysulfone), PVA (polyvinylalcohol), PVCi (polyvinylcinnamate), TAC (triacetylcellulose), polysilicone (polysilicone), polyurethane (polyurethane), epoxy resin (epoxy Resin) and the like can be used. Preferably, the transmittance is 96-99.9% in the light source of 500 nm wavelength.

다음으로 배면 지지체 (103)에 붙어있는, 원판몰드 (101)의 패턴이 전사된 경화 고분자 수지 (102b)를 원판몰드 (101)로부터 이형시킨다 (단계 3).Next, the cured polymer resin 102b to which the pattern of the disc mold 101 transferred to the back support 103 is transferred from the disc mold 101 (step 3).

상기 이형된 경화 고분자 수지 (102b)의 일면에는 원판몰드 (101)로부터 전사된 패턴이 형성되어 있다.A pattern transferred from the disc mold 101 is formed on one surface of the release cured polymer resin 102b.

선택적으로 상기 패턴이 형성된 경화 고분자 수지 (102b) 몰드를 에이징시킴으로써 성형 몰드 (104)를 완성한다(단계 4). Optionally, the molding mold 104 is completed by aging the cured polymer resin 102b mold on which the pattern is formed (step 4).

이때 에이징이란 패턴이 형성된 경화 고분자 수지 몰드의 표면을 자외선에 과다하게 노출시켜 몰드의 경도를 향상시키는 동시에 자외선에 대한 잔여 반응기를 완전 소멸시키거나, 열처리를 통하여 잔여 반응기를 소멸시킴과 동시에 표면 평도 및 지지체와의 접착력을 더욱 향상시키는 과정을 의미한다. 여기서 에이징 단계는 몰드의 표면을 자외선에 과다하게 노출시켜 몰드의 경도를 향상시키는 공정이 바람직하며, 노광과 열처리 중 한 가지를 선택하여 실시하거나 또는 둘 모두를 단계적으로 진행할 수 있다.In this case, aging means that the surface of the cured polymer resin mold on which the pattern is formed is excessively exposed to ultraviolet rays to improve the hardness of the mold and to completely extinguish the remaining reactors against ultraviolet rays or to extinguish the remaining reactors through heat treatment and at the same time, the surface flatness. And it means a process for further improving the adhesion with the support. Here, the aging step is preferably a process of improving the hardness of the mold by excessively exposing the surface of the mold to ultraviolet rays, may be carried out by selecting one of the exposure and the heat treatment, or both may be carried out step by step.

상기와 같이 본 발명에 따른 방법에 의해 높은 완성도를 갖는 몰드를 제조할 수 있다.As described above, a mold having a high degree of completeness can be produced by the method according to the present invention.

또한 본 발명의 광경화형 수지 몰드 조성물을 이용하여 제조된 상기 몰드를 이용하여 반도체, 디스플레이를 포함하는 각종 전자 디바이스 산업 공정에 필요한 미세 패턴을 안정적이고 용이하게 형성할 수 있다.In addition, by using the mold manufactured using the photocurable resin mold composition of the present invention, it is possible to stably and easily form fine patterns required for various electronic device industrial processes including semiconductors and displays.

또한 상기 몰드를 이용한 임프린트 리소그래피 공정이, 종래 미세 패턴 형성을 위한 포토 리소그래피 공정을 대체함으로써 기존 포토리소그래피 공정의 노광, 현상, 세정 등의 여러 단계를 단순화 할 수 있을 뿐만 아니라, 제조 공정 시간 (tact time)을 단축하여, 제조원가를 절감하고 생산성을 향상시킬 수 있다.In addition, the imprint lithography process using the mold replaces the conventional photolithography process for forming a fine pattern, thereby simplifying various steps such as exposure, development, and cleaning of the existing photolithography process, and also a manufacturing time (tact time). ), The manufacturing cost can be reduced and the productivity can be improved.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

합성예: 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산의 제조Synthesis Example: Preparation of polyaliphatic aromatic silsesquioxane containing ethylenically unsaturated group and fluorine group

[합성예 1-a] Synthesis Example 1-a

냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 15 중량부, 메탄올(순도 99.86 %) 85 중량부, 테트라메틸암모늄하이드록사이드(순도 25 %) 1 중량부, 트리메톡시페닐실란(다우코닝사, 상품명 DOW CORNING(R) Z-6124 SILANE) 20 중량부, 감마-메타아크릴옥시프로필트리메톡시실란(다우코닝사, 상품명 DOW CORNING(R) Z-6030 SILANE) 35 중량부, 메틸트리메톡시 실란(다우코닝사, 상품명 DOW CORNING(R) Z-6300 SILANE) 70 중량부 및 퍼플루오르옥틸트리에톡시실란(다이나실란. 상품명 DYNASYLAN(R) F-8261) 10 중량부를 넣고, 질소 분위기에서 서서히 8시간 동안 교반 후 디클로로메탄(순도 99.5%, 동양제철화학) 150 중량부를 투입하여 2시간 추가 교반하였다. In a dried flask equipped with a cooling tube and a stirrer, 15 parts by weight of distilled water, 85 parts by weight of methanol (99.86% purity), 1 part by weight of tetramethylammonium hydroxide (25% purity), trimethoxyphenylsilane (Dow Corning) , 20 parts by weight of DOW CORNING (R) Z-6124 SILANE), 35 parts by weight of gamma-methacryloxypropyltrimethoxysilane (Dow Corning, trade name DOW CORNING (R) Z-6030 SILANE), methyltrimethoxy silane (Dow Corning, DOW CORNING (R) Z-6300 SILANE) 70 parts by weight and 10 parts by weight of perfluorooctyltriethoxysilane (dynasilane, trade name DYNASYLAN (R) F-8261) were added, and gradually After stirring for 150 parts by weight of dichloromethane (purity 99.5%, Dongyang Steel Chemical) was added and stirred for 2 hours.

교반된 액을 증류수로 수 차례 세정분별하여 불순물을 제거한 후, 상기 세정된 액체를 상온에서 20시간이상 진공건조하여 스티렌 환산분자량 25,000의 목적하는 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a)을 제조하였다.The stirred liquid was washed with distilled water several times to remove impurities, and then the dried liquid was vacuum-dried at room temperature for 20 hours or more to obtain a polyaliphatic aromatic silsesqui containing a desired ethylenically unsaturated group and a fluorine group having a molecular weight of 25,000 styrene. Oxane 1a was prepared.

[합성예 1-b] Synthesis Example 1-b

냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 15 중량부, 메탄올(순도 99.86 %) 85 중량부, 테트라메틸암모늄하이드록사이드(순도 25 %) 1 중량부, 트리메톡시페닐실란(다우코닝사, 상품명 DOW CORNING(R) Z-6124 SILANE) 20 중량부, 감마-메타아크릴옥시프로필트리메톡시실란(다우코닝사, 상품명 DOW CORNING(R) Z-6030 SILANE) 70 중량부, 메틸트리메톡시 실란(다우코닝사, 상품명 DOW CORNING(R) Z-6300 SILANE) 30 중량부 및 퍼플루오르옥틸트리에톡시실란(다이나실란. 상품명 DYNASYLAN(R) F-8261) 30 중량부를 넣고, 질소 분위기에서 서서히 8시간 동안 교반후 디클로로메탄(순도 99.5%, 동양제철화학) 150 중량부를 투입하여 2시간 추가 교반하였다.In a dried flask equipped with a cooling tube and a stirrer, 15 parts by weight of distilled water, 85 parts by weight of methanol (99.86% purity), 1 part by weight of tetramethylammonium hydroxide (25% purity), trimethoxyphenylsilane (Dow Corning) , 20 parts by weight of DOW CORNING (R) Z-6124 SILANE), 70 parts by weight of gamma-methacryloxypropyltrimethoxysilane (Dow Corning, DOW CORNING (R) Z-6030 SILANE), methyltrimethoxy silane (30 parts by weight of Dow Corning, DOW CORNING (R) Z-6300 SILANE) and 30 parts by weight of perfluorooctyltriethoxysilane (dynasilane. Trademark DYNASYLAN (R) F-8261) were gradually added under nitrogen atmosphere for 8 hours. After stirring for 150 parts by weight of dichloromethane (purity 99.5%, Dongyang Steel Chemical) was added and stirred for 2 hours.

교반된 액을 증류수로 수차례 세정분별하여 불순물을 제거한 후, 상기 세정된 액체를 상온에서 20시간이상 진공건조하여 스티렌 환산분자량 25,000의 목적하는 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1b)을 제조하였다.The stirred liquid was washed several times with distilled water to remove impurities, and then the washed liquid was vacuum-dried at room temperature for 20 hours or more to obtain a polyaliphatic aromatic silsesqui including a desired ethylenically unsaturated group and a fluorine group having a styrene equivalent molecular weight of 25,000. Oxane 1b was prepared.

[실시예 1]Example 1

상기 [합성예 1-a]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 30 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 23 중량부, 메타아크릴산글리시딜 23 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 24 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조하였다.30 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing the ethylenically unsaturated group and the fluorine group obtained in Synthesis Example 1-a, 23 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 23 parts by weight of dill and 24 parts by weight of (3-glycidoxy propyl) trimethoxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator was added at room temperature to 300-400 rpm. The mixture was stirred uniformly for 20 hours to prepare a transparent liquid resin solution 102a.

그 다음, 도 1에 나타난 바와 같이, 원판 스탬프(101)의 패턴이 위로 향하도록 하고, 상기 제조한 광경화형 수지 몰드 조성물(102a)을 그 두께가 100 ㎛가 되도록 슬릿 코팅하였다. 광경화형 수지 몰드 조성물이 도포된 원판 몰드 위로 배면 지지체(103)를 합착한 후 질소 분위기에서 자외선을 조사하여 경화시키고, 원판 스탬프(101)의 패턴이 전사된 경화 고분자 수지(102b)가 붙어있는 배면 지지체(103)를 원판 스탬프(101)로부터 이형하였다. 상기 점착된 경화 고분자 수지(102b)의 완전 경화를 위해 자외선을 과조사하였다. 또한 배면 지지체(103)의 완전한 접착을 위해 100 ℃의 컨벤션 오븐(convection oven)에 넣어 추가적으로 1 시간 동안 열을 가하여 최종 고분자 수지 몰드(104)를 완성하였다.Then, as shown in FIG. 1, the pattern of the disc stamp 101 was faced upward, and the photocurable resin mold composition 102a prepared above was slit-coated so that its thickness became 100 µm. The back support 103 is bonded onto the disc mold to which the photocurable resin mold composition is applied, and then irradiated with ultraviolet rays in a nitrogen atmosphere to cure, and the back side on which the cured polymer resin 102b to which the pattern of the disc stamp 101 is transferred is attached. The support body 103 was released from the original stamp 101. Ultraviolet rays were irradiated for complete curing of the adhesive cured polymer resin 102b. In addition, in order to completely adhere the back support 103, it was put in a convention oven at 100 ° C. and heated for an additional hour to complete the final polymer resin mold 104.

[실시예 2]Example 2

상기 [합성예 1-a]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 64 중량부, 메타아크릴산글리시딜 18 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 18 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.64 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-a, 18 parts by weight of glycidyl methacrylate and (3-glycidoxy propyl) tree 18 parts by weight of methoxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator and uniformly stirred at 300-400 rpm at room temperature for 20 hours to provide a transparent liquid resin solution (102a) A polymer resin mold was prepared in the same manner as in Example 1, except that) was prepared.

[실시예 3]Example 3

상기 [합성예 1-a]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 55 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 15 중량부, 메타아크릴산글리시딜 15 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 15 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.55 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-a, 15 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 15 parts by weight of dill and 15 parts by weight of (3-glycidoxypropyl) trimethoxysilane, and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator at room temperature at 300-400 rpm A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.

[실시예 4]Example 4

상기 [합성예 1-a]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 70 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 10 중량부, 메타아크릴산글리시딜 10 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 10 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.70 parts by weight of the polyaliphatic aromatic silsesquioxane (1a) containing the ethylenically unsaturated group and the fluorine group obtained in Synthesis Example 1-a, 10 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 10 parts by weight of dill and 10 parts by weight of (3-glycidoxy propyl) trimethoxysilane, and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator at 300-400 rpm A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.

[실시예 5]Example 5

상기 [합성예 1-b]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1b) 30 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 23 중량부, 메타아크릴산글리시딜 23 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 24 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.30 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing the ethylenically unsaturated group and the fluorine group obtained in Synthesis Example 1-b, 23 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 23 parts by weight of dill and 24 parts by weight of (3-glycidoxy propyl) trimethoxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator was added at room temperature to 300-400 rpm. A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.

[실시예 6]Example 6

상기 [합성예 1-b]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1b) 54 중량부, 메타아크릴산글리시딜 23 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 23 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.54 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-b, 23 parts by weight of glycidyl methacrylate and (3-glycidoxy propyl) tree 23 parts by weight of methoxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator, and uniformly stirred at 300-400 rpm for 20 hours at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that) was prepared.

[실시예 7]Example 7

상기 [합성예 1-b]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1b) 55 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 15 중량부, 메타아크릴산글리시딜 15 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 15 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.55 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-b, 15 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 15 parts by weight of dill and 15 parts by weight of (3-glycidoxypropyl) trimethoxysilane, and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator at room temperature at 300-400 rpm A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.

[실시예 8]Example 8

상기 [합성예 1-b]에서 얻어진 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1b) 70 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 10 중량부, 메타아크릴산글리시딜 10 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 10 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.70 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-b, 10 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and glycerin methacrylate 10 parts by weight of dill and 10 parts by weight of (3-glycidoxy propyl) trimethoxysilane, and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator at 300-400 rpm A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring for 20 hours.

[비교예 1]Comparative Example 1

에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산를 사용하지 않고 2-(퍼플루오르헥실)에틸아크릴레이트 33 중량부, 메타아크릴산글리시딜 33 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 34 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.33 parts by weight of 2- (perfluorohexyl) ethyl acrylate, 33 parts by weight of glycidyl methacrylate, and (3-glycidoxy propyl) tree without using a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group 34 parts by weight of methoxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator, and uniformly stirred at 300-400 rpm for 20 hours at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that) was prepared.

[비교예 2]Comparative Example 2

상기 [합성예 1-a]에서 얻어진 에틸렌성 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 10 중량부, 2-(퍼플루오르헥실)에틸아크릴레이트 30 중량부, 메타아크릴산글리시딜 30 중량부 및 (3-글리시드옥시프로필)트리메톡시실레인 30 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.10 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenic ethylenically unsaturated group and fluorine group obtained in Synthesis Example 1-a, 30 parts by weight of 2- (perfluorohexyl) ethyl acrylate, and methacrylic acid 30 parts by weight of glycidyl and 30 parts by weight of (3-glycidoxypropyl) trimethoxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added at room temperature to 300-. A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring at 400 rpm for 20 hours.

[비교예 3]Comparative Example 3

상기 [합성예 1-a]에서 얻어진 에틸렌성 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산(1a) 100 중량부, 광개시제로 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트 1 중량부를 투입하여 상온에서 300-400rpm으로 20시간동안 균일하게 교반하여 투명한 액상의 수지용액(102a)을 제조한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 수지몰드를 제조하였다.100 parts by weight of the polyaliphatic aromatic silsesquioxane (1a) containing the ethylenic ethylenically unsaturated group and the fluorine group obtained in Synthesis Example 1-a, and ethyl (2,4,6-trimethylbenzoyl) phenylphosphide as a photoinitiator. A polymer resin mold was prepared in the same manner as in Example 1, except that 1 part by weight of nate was added and stirred uniformly at 300-400 rpm for 20 hours at room temperature to prepare a transparent liquid resin solution 102a. It was.

[비교예 4][Comparative Example 4]

상기 실시예 1에서 제조한 광경화형 수지 조성물 대신에 종래 고분자 수지 몰드의 재료인 PDMS(다우코닝(Dow-Corning)사제, sylgard(R) 184 silicone elastomer kit)를 상기 실시예 1과 같이 원판몰드(101)에 100 ㎛ 두께로 도포하고 60 ℃의 오븐에서 180 분 동안 소성시켜 경화한 후, 원판몰드로부터 경화된 수지를 이형하여 고분자 수지 몰드를 제조하였다.Instead of the photocurable resin composition prepared in Example 1, PDMS (Dow-Corning, sylgard (R) 184 silicone elastomer kit), which is a material of a conventional polymer resin mold, was prepared in the same manner as in Example 1 101) was applied to a thickness of 100 μm and cured by baking in an oven at 60 ° C. for 180 minutes, and then the cured resin was released from the disc mold to prepare a polymer resin mold.

[시험예 1][Test Example 1]

상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지 몰드를 이용하여 하기와 같은 방법으로 접촉각, 이형성, 내화학성 및 투과율을 측정하고, 그 결과를 하기 표 1에 나타내었다.Using the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4, contact angles, mold release properties, chemical resistance, and transmittance were measured in the following manner, and the results are shown in Table 1 below.

가) 젖음성 - 상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지 몰드의 표면에 물방울을 떨어뜨려 제조된 수지몰드의 표면과 물방울 사이의 접촉각을 5회 측정하여 그 평균값을 기재하였다.A) wettability-5 times the contact angle between the surface of the resin mold and water droplets prepared by dropping water droplets on the surface of the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4 and describing the average value It was.

나) 이형성 : 상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지 몰드에 적량의 광경화제가 배합된 일반 상용화 아크릴계 수지를 전면에 도포한 후 글라스를 덮어 자외선 램프로 완전히 경화시키고, 상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지몰드와 경화된 아크릴계 수지의 계면을 손으로 당겨 이형하였다.B) Release property: After applying the commercially available acrylic resin containing a suitable amount of photocuring agent to the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4 on the entire surface, the glass was completely cured with an ultraviolet lamp. , By pulling the interface between the polymer resin mold and the cured acrylic resin prepared in Examples 1 to 8, and Comparative Examples 1 to 4 by hand.

이때, 손으로 이형이 가능한 경우 ◎, 커터칼 등의 도구로 계면사이에 공간을 확보해야만 이형이 이루어지는 경우 ○, 이형이 전혀 이루어지지 않을 경우 △, 상기 실시예 1 내지 8 및 비교예 1 내지 4에서 제조한 고분자 수지몰드 또는 경화된 아크릴계 수지의 일부 또는 전부가 파손되어 떨어지는 경우 X로 표에 기재하였다.At this time, when the release is possible by hand ◎, when release is achieved only by securing a space between interfaces with a tool such as a cutter knife ○, when the release is not made at all △, Examples 1 to 8 and Comparative Examples 1 to 4 Some or all of the polymer resin molds or cured acrylic resins prepared in the above are broken and listed in the table as X.

다) 내화학성 : 아세톤에 상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지 몰드를 완전히 침적하고 7일을 방치한 후 수지 몰드의 중량변화를 측정하였다. C) Chemical resistance: After the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4 were completely deposited on acetone and left for 7 days, the weight change of the resin mold was measured.

측정결과, 초기 대비 중량의 변화비가 0-1 %인 경우 ◎, 1-3 %인 경우 ○, 3-5 % 이상인 경우 △, 5% 이상인 경우 X로 표에 기재하였다.As a result of the measurement, when the change ratio of the weight to the initial stage is 0-1%, ◎, 1-3% are ○, 3-5% or more △, 5% or more are listed in the table.

라) 광투과율 : 상기 실시예 1 내지 8, 및 비교예 1 내지 4에서 제조한 고분자 수지 몰드에 대하여 가시광선의 광흡수 스펙트럼(spectrum)을 측정하고, 400 ㎚에 있어서 광선 투과율을 측정하여 기재하였다.D) Light transmittance: The light absorption spectrum of visible light was measured for the polymer resin molds prepared in Examples 1 to 8 and Comparative Examples 1 to 4, and the light transmittance was measured and described at 400 nm.

표 1 접촉각 이형성 내화학성 광투과율 실시예 1 101 ○ ○ 97.5 실시예 2 102 ○ ○ 97.7 실시예 3 103 ○ ◎ 98.7 실시예 4 105 ◎ ◎ 96.3 실시예 5 104 ○ ◎ 97.0 실시예 6 104 ○ ○ 97.1 실시예 7 107 ◎ ◎ 98.8 실시예 8 109 ◎ ◎ 97.4 비교예 1 81 X X 95.8 비교예 2 92 X △ 96.3 비교예 3 114 △ △ 97.2 비교예 4 105 ◎ X 98.4 Table 1 Contact angle Dysplasia Chemical resistance Light transmittance Example 1 101 ○ ○ 97.5 Example 2 102 ○ ○ 97.7 Example 3 103 ○ ◎ 98.7 Example 4 105 ◎ ◎ 96.3 Example 5 104 ○ ◎ 97.0 Example 6 104 ○ ○ 97.1 Example 7 107 ◎ ◎ 98.8 Example 8 109 ◎ ◎ 97.4 Comparative Example 1 81 X X 95.8 Comparative Example 2 92 X △ 96.3 Comparative Example 3 114 △ △ 97.2 Comparative Example 4 105 ◎ X 98.4

상기 표 1에 나타난 바와 같이, 상기 표 1에 나타난 바와 같이, 본 발명의 광경화형 수지 몰드 조성물을 이용하여 제조한 실시예 1 내지 8의 불소 함유 실세스퀴옥산 고분자 수지 몰드는 비교예 1 내지 4와 비교하여 접촉각, 이형성, 투과율이 동등 수준 내지 이상으로 나타났으며, 특히 내화학성면에서 탁월함을 확인할 수 있었다. As shown in Table 1, as shown in Table 1, the fluorine-containing silsesquioxane polymer resin molds of Examples 1 to 8 prepared using the photocurable resin mold composition of the present invention are Comparative Examples 1 to 4 Compared with, the contact angle, release property, and transmittance were found to be at the same level or higher, and in particular, the chemical resistance was excellent.

본 발명에 따른 광경화형 수지 몰드 조성물은 임프린트 리소그래피 몰드에 적용되어 원판 스탬프 표면의 이형제 처리 여부와 상관없이 원판 스탬프와의 우수한 이형성으로 고가의 원판 스탬프가 오손되는 것을 막을 수 있을 뿐만 아니라, 패턴형성을 위한 열경화 또는 광경화 수지에 대해 젖음성이 우수하며, 특히 내화학성 및 내구성이 우수하여 반도체, 디스플레이 등을 포함하는 각종 전자 디바이스 제조에 필요한 미세패턴을 보다 빠르고 안정적으로 제작할 수 있다.The photocurable resin mold composition according to the present invention can be applied to an imprint lithography mold to prevent expensive original stamps from being damaged by excellent release from the original stamps, regardless of whether the original stamps are treated with a release agent, or to prevent pattern formation. It is excellent in the wettability to the thermosetting or photo-curing resin for, in particular, excellent in chemical resistance and durability, it is possible to produce a fine pattern required for manufacturing various electronic devices including semiconductors, displays, etc. more quickly and stably.

Claims (15)

(1) 하기 화학식 1의 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산;(1) a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group represented by the following Formula 1; (2) 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머;(2) reactive monomers comprising at least one unsaturated group in the molecule; (3) 하기 화학식 2의 유기실란계 화합물 및(3) an organosilane compound of Formula 2 and (4) 광개시제(4) photoinitiator 를 포함하는 것을 특징으로 하는 광경화형 수지 조성물:Photocurable resin composition comprising: [화학식 1][Formula 1]
Figure PCTKR2012005657-appb-I000004
Figure PCTKR2012005657-appb-I000004
 상기 식에서,Where R1 내지 R4는 각각 독립적으로 수소원자; C2-20의 에틸렌성 불포화기, 불소 또는 C6-20의 방향족기로 치환되거나 치환되지 않은 C1-20의 알킬기 또는 알콕시기를 나타내고, 이때 R1 내지 R4 중 적어도 하나 이상은 상기 에틸렌성의 불포화기를 포함하는 C1-20의 알킬기 또는 알콕시기이고, 또한 R1 내지 R4 중 적어도 하나 이상은 불소를 포함하는 C1-20의 알킬기 또는 알콕시기이고,ROne To R4Each independently represent a hydrogen atom; C2-20Of ethylenically unsaturated groups, fluorine or C6-20Unsubstituted or substituted with an aromatic group1-20of Alkyl group or alkoxy group, where ROne To R4At least one of C includes the ethylenically unsaturated group1-20of Alkyl group or alkoxy group, and ROne To R4At least one of C contains fluorine1-20of An alkyl group or an alkoxy group, n은 1-30의 정수이며,n is an integer from 1-30, R5 내지 R8은 각각 독립적으로 수소원자, C1-20의 알킬기 또는 알콕시기이다.R 5 to R 8 are each independently a hydrogen atom, an alkyl group of C 1-20 or an alkoxy group. [화학식 2][Formula 2] R9 4-m-Qp-Si-(OR10)m R 9 4-m -Q p -Si- (OR 10 ) m 상기 식에서,Where R9는 페닐기, 아미노기, (메타)아크릴기, 비닐기, 에폭시기 및 이들의 조합으로 이루어진 군에서 선택되고,R 9 is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof, R10은 C1-5의 알킬기, C3-10의 시클로알킬기, C6-12의 아릴기, -OCR', -CR'=N-OH 및 이들의 조합으로 이루어진 군에서 선택되며,R 10 is selected from the group consisting of an alkyl group of C 1-5 , a cycloalkyl group of C 3-10 , an aryl group of C 6-12 , -OCR ', -CR' = N-OH, and a combination thereof, 이때 R'은 C1-6의 알킬기이고,Wherein R 'is an alkyl group of C 1-6 , Q는 C2-6의 알킬렌기 또는 C2-6 알킬렌옥시기이고,Q is a C 2-6 alkylene group or C 2-6 alkyleneoxy group, m은 0 내지 4의 정수이며,m is an integer from 0 to 4, p는 0 또는 1의 정수이다.p is an integer of 0 or 1. 제1항에 있어서,The method of claim 1, 상기 광경화형 수지 조성물은,The photocurable resin composition, (1) 하기 화학식 1의 에틸렌성 불포화기와 불소기를 포함하는 폴리지방족방향족 실세스퀴옥산 30 내지 80 중량부;(1) 30 to 80 parts by weight of a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group represented by the following Formula 1; (2) 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머 5 내지 50 중량부;(2) 5 to 50 parts by weight of a reactive monomer comprising at least one unsaturated group in the molecule; (3) 하기 화학식 2의 유기실란계 화합물 5 내지 50 중량부; 및(3) 5 to 50 parts by weight of the organosilane compound of Formula 2; And (4) 상기 (1), (2), 및 (3)성분의 총 합계량 100 중량부에 대하여 광개시제 0.1 내지 10 중량부;(4) 0.1 to 10 parts by weight of the photoinitiator based on 100 parts by weight of the total amount of the components (1), (2), and (3); 를 포함하는 것을 특징으로 하는 광경화형 수지 조성물.Photocurable resin composition comprising a. 제1항에 있어서,The method of claim 1, 상기 (1)의 폴리지방족방향족 실세스퀴옥산이, 중량평균분자량 1,000 내지 200,000의 래더 (Ladder) 내지 케이지 (Cage) 구조의 화합물인 것을 특징으로 하는 광경화형 수지 조성물.The polyaliphatic aromatic silsesquioxane of the above (1) is a compound having a ladder to cage structure with a weight average molecular weight of 1,000 to 200,000. 제1항에 있어서,The method of claim 1, 상기 광경화성 수지 조성물이 분자 내에 하나 이상의 불소기를 포함하는 반응성 모노머를 더욱 포함하는 것을 특징으로 하는 광경화형 수지 조성물.The photocurable resin composition further comprises a reactive monomer containing at least one fluorine group in the molecule. 제4항에 있어서, The method of claim 4, wherein 상기 불소기를 포함하는 반응성 모노머가, 퍼플루오로헥실에틸렌, 1,4-디비닐도데카플루오로헥산, 3-퍼플루오로부틸하이드록시프로필메타크릴레이트, 3-퍼플루오로헥실하이드록실프로필메타크릴레이트, 트리플루오로에틸메타크릴레이트, 테트라플루오로프로필메타크릴레이트, 2-퍼플루오로헥실에틸아크릴레이트, 3-퍼플루오로메틸부틸-2-하이드록시프로필아크릴레이트 및 그 유도체로 이루어진 군에서 1종 이상 선택되는 것을 특징으로 하는 광경화형 수지 조성물.Reactive monomers containing the fluorine group include perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropyl methacrylate, and 3-perfluorohexylhydroxypropyl methacrylate. Group consisting of acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, 2-perfluorohexylethyl acrylate, 3-perfluoromethylbutyl-2-hydroxypropyl acrylate and its derivatives Photocurable resin composition, characterized in that at least one selected from. 제1항에 있어서,The method of claim 1, 상기 (2)의 분자 내에 하나 이상의 불포화기를 포함하는 반응성 모노머가, 하나 이상의 불포화기와 함께 (메타)아크릴기, 또는 에폭시기를 포함하는 반응성 모노머인 것을 특징으로 하는 광경화형 수지 조성물.A photocurable resin composition, wherein the reactive monomer containing at least one unsaturated group in the molecule of (2) is a reactive monomer containing a (meth) acryl group or an epoxy group together with at least one unsaturated group. 제6항에 있어서,The method of claim 6, 상기 (메타)아크릴기를 포함하는 반응성 모노머가, 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 시클로헥실 메타크릴레이트, 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트 및 1,6-헥산디올디아크릴레이트로 이루어진 군에서 1종 이상 선택되는 것을 특징으로 하는 광경화형 수지 조성물.The reactive monomer containing the said (meth) acryl group is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert- butyl methacrylate, methyl acrylate, isopropyl acryl Latex, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl Acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, Isoboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate Photocurable resin composition, characterized in that at least one member selected from the group consisting of ethane and 1,6-hexanediol diacrylate. 제6항에 있어서,The method of claim 6, 상기 에폭시기를 포함하는 반응성 모노머가, 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, 아크릴산-β-에틸글리시딜, 메타크릴산-β-에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, 아크릴산-3,4-에폭시 시클로헥실메틸, 메타크릴산-3,4-에폭시 시클로헥실메틸, 4-비닐시클로헥센옥사이드, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르 및 p-비닐벤질글리시딜에테르로 이루어진 군에서 1종 이상 선택되는 것을 특징으로 하는 광경화형 수지 조성물.The reactive monomer containing the said epoxy group is glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethyl acrylate, glycidyl (alpha)-n-propyl acrylate, glycidyl (alpha)-n-butylacrylate, acrylic acid β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacryl Acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxy cyclohexyl Consisting of methyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether Photocurable resin composition, characterized in that at least one selected from the group. 제1항에 있어서,The method of claim 1, 상기 (3)의 유기실란계 화합물이, 페닐기, 아미노기, (메타)아크릴기, 비닐기 또는 에폭시기를 포함하는 유기 실란계 화합물인 것을 특징으로 하는 광경화형 수지 조성물.The organosilane compound of the above (3) is an organosilane compound comprising a phenyl group, an amino group, a (meth) acryl group, a vinyl group or an epoxy group. 제9항에 있어서,The method of claim 9, 상기 유기실란계 화합물이, (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3-(메타아크릴옥시)프로필트리메톡시실란, 3,4-에폭시부틸트리메톡시실란, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 아미노프로필트리에톡시실란, 비닐트리에톡시실란, 비닐트리-t-부톡시실란, 비닐트리이소부톡시실란, 비닐트리이소프로폭시실란, 비닐트리페녹시실란, 페닐트리에톡시실란, 페닐트리메톡시실란, 아미노프로필트리메톡시실란 및 N-페닐-3-아미노프로필트리메톡시실란으로 이루어진 군에서 1종 이상 선택되는 것을 특징으로 하는 광경화형 수지 조성물.The said organosilane type compound is (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxysilane, (3-glycidoxy propyl) methyldimethoxysilane, (3-gly Seedoxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, Vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane Photocurable resin composition, characterized in that at least one selected from the group consisting of. 제1항에 있어서,The method of claim 1, 상기 (4) 광개시제가 다이페닐-(2,4,6-트리메틸벤조일)포스핀옥사이드, 메틸벤조일포르메이트, 에틸(2,4,6-트리메틸벤조일)페닐포스피네이트, 2,4-비스트리클로로메틸-6-p-메톡시스티릴-s-트리아진, 2-p-메톡시스티릴-4,6-비스트리클로로메틸-s-트리아진, 2,4-트리클로로메틸-6-트리아진, 2,4-트리클로로메틸-4-메틸나프틸-6-트리아진, 벤조페논, p-(다이에틸아미노)벤조페논, 2,2-다이클로로-4-페녹시아세토페논, 2,2-다이에톡시아세토페논, 2-도데실티오크산톤, 2,4-다이메틸티오크산톤, 2,4-다이에틸티오크산톤, 및 2,2-비스-2-클로로페닐-4,5,4,5-테트라페닐-2-1,2-다이이미다졸로 이루어진 군에서 1종 이상 선택되는 것을 특징으로 하는 광경화형 수지 조성물.Said (4) photoinitiator is diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoyl formate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloro Romethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6- Triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2 , 2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,2-bis-2-chlorophenyl-4, Photocurable resin composition, characterized in that at least one selected from the group consisting of 5,4,5-tetraphenyl-2-1,2-diimidazole. 제1항에 있어서,The method of claim 1, 상기 광경화성 수지 조성물이 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르 및 이들의 혼합물로 이루어진 군에서 선택되는 계면활성제를 추가로 포함하는 것을 특징으로 하는 임프린트 리소그래피용 광경화형 수지 조성물.The photocurable resin composition for imprint lithography, wherein the photocurable resin composition further comprises a surfactant selected from the group consisting of polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and mixtures thereof. 제1항에 있어서,The method of claim 1, 상기 광경화성 수지 조성물이 임프린트 리소그래피용 몰드용인 것을 특징으로 하는 광경화형 수지 조성물.The said photocurable resin composition is for the mold for imprint lithography, The photocurable resin composition characterized by the above-mentioned. (1) 패턴이 형성된 원판 스탬프 일면에 제1항에 따른 임프린트 리소그래피용 광경화형 수지 조성물을 도포하고 경화시켜 원판 몰드의 패턴이 전사된 경화 고분자 수지를 제조하는 단계, 및(1) coating and curing the photocurable resin composition for imprint lithography according to claim 1 on one surface of the original stamp on which the pattern is formed to produce a cured polymer resin to which the pattern of the original mold is transferred; and (2) 상기 패턴이 전사된 경화 고분자 수지를 원판 몰드로부터 이형시키는 단계를 포함하는, 임프린트 몰드의 제조방법.(2) A method for producing an imprint mold, comprising the step of releasing the cured polymer resin to which the pattern is transferred from a disc mold. 제14항에 따른 제조방법에 의해 제조된 임프린트 몰드.An imprint mold manufactured by the manufacturing method according to claim 14.
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CN114690563A (en) * 2022-05-05 2022-07-01 潍坊星泰克微电子材料有限公司 Photoresist for nanoimprinting process, preparation method and application thereof

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KR101751411B1 (en) * 2016-02-19 2017-07-11 엘티씨 (주) Poly silsesquinoxane resin composition and black resist composition for light-shielding comprising same
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CN114690563A (en) * 2022-05-05 2022-07-01 潍坊星泰克微电子材料有限公司 Photoresist for nanoimprinting process, preparation method and application thereof

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