[go: up one dir, main page]

WO2013012230A2 - Composition de résine photodurcissable - Google Patents

Composition de résine photodurcissable Download PDF

Info

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
Authority
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
Other languages
English (en)
Korean (ko)
Other versions
WO2013012230A3 (fr
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
Original Assignee
Dongjin Semichem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of WO2013012230A2 publication Critical patent/WO2013012230A2/fr
Publication of WO2013012230A3 publication Critical patent/WO2013012230A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition de résine photodurcissable et, plus particulièrement, une composition de résine photodurcissable qui peut être appliquée sur un moule d'impression lithographique et qui se détache plus facilement d'un tampon de disque même si la surface dudit tampon de disque n'est pas traitée avec un antiadhésif, ce qui permet d'éviter la contamination du tampon de disque coûteux. En outre, la résistance aux produits chimiques et la durabilité de la composition de résine selon l'invention sont excellentes, ce qui permet de produire rapidement et de manière stable des micromotifs nécessaires pour fabriquer divers dispositifs électroniques, tels que des semi-conducteurs et des écrans d'affichage.
PCT/KR2012/005657 2011-07-19 2012-07-16 Composition de résine photodurcissable Ceased WO2013012230A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0071298 2011-07-19
KR1020110071298A KR101820087B1 (ko) 2011-07-19 2011-07-19 광경화형 수지 조성물

Publications (2)

Publication Number Publication Date
WO2013012230A2 true WO2013012230A2 (fr) 2013-01-24
WO2013012230A3 WO2013012230A3 (fr) 2013-06-13

Family

ID=47558598

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/005657 Ceased WO2013012230A2 (fr) 2011-07-19 2012-07-16 Composition de résine photodurcissable

Country Status (2)

Country Link
KR (1) KR101820087B1 (fr)
WO (1) WO2013012230A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114690563A (zh) * 2022-05-05 2022-07-01 潍坊星泰克微电子材料有限公司 用于纳米压印工艺的光刻胶及其制备方法和应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101751411B1 (ko) * 2016-02-19 2017-07-11 엘티씨 (주) 폴리실세스퀴옥산 수지 조성물 및 이를 포함하는 차광용 블랙 레지스트 조성물
KR20230126307A (ko) 2022-02-22 2023-08-30 삼성디스플레이 주식회사 수지 조성물, 및 이를 포함한 디스플레이 장치

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006328231A (ja) * 2005-05-26 2006-12-07 Nagase Chemtex Corp 光素子用封止樹脂組成物
US8080604B2 (en) * 2007-03-02 2011-12-20 Lintec Corporation Adhesive containing ladder-type polysilsesquioxane and adhesive sheet
JP5425406B2 (ja) * 2007-06-29 2014-02-26 リンテック株式会社 ポリシルセスキオキサン化合物からなる成形材料、封止材および光素子封止体
JP5435879B2 (ja) * 2008-02-14 2014-03-05 株式会社ダイセル ナノインプリント用硬化性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114690563A (zh) * 2022-05-05 2022-07-01 潍坊星泰克微电子材料有限公司 用于纳米压印工艺的光刻胶及其制备方法和应用

Also Published As

Publication number Publication date
WO2013012230A3 (fr) 2013-06-13
KR101820087B1 (ko) 2018-01-18
KR20130010583A (ko) 2013-01-29

Similar Documents

Publication Publication Date Title
KR101708256B1 (ko) 나노 임프린트용 레지스트 하층막 형성 조성물
EP2370998B1 (fr) Procede de fabrication de materiaux a motifs
JP6117783B2 (ja) 光硬化型有機−無機ハイブリッド樹脂組成物
WO2011099777A2 (fr) Feuille pour la formation de revêtement dur
US20090295041A1 (en) Printing form precursor and process for preparing a stamp from the precursor
WO2011016651A9 (fr) Composition de résine photodurcissable pour lithographie d'impression et procédé de fabrication d'un moule d'impression l'utilisant
CN104870198A (zh) 图案化的结构化转印带
WO2011099766A2 (fr) Procédé de formation de revêtement superficiel dur
WO2011099778A2 (fr) Composite de résine pour la formation de couche de revêtement dur
TW201922815A (zh) 電路配線的製造方法、觸控面板的製造方法及附圖案基材的製造方法
WO2013191341A1 (fr) Procédé de fabrication d'un poinçon pour un appareil de nanolithographie plasmonique, et appareil de nanolithographie plasmonique
WO2011007979A2 (fr) Composition de résine photodurcissable fluorée, et procédé de production d'un moule en résine au moyen de cette composition
WO2018097580A1 (fr) Photo-initiateur et composition de résine photosensible de protection contre la lumière le contenant
WO2010123162A1 (fr) Procédé de formation de microstructure hiérarchisée, par durcissement partiel
WO2013012230A2 (fr) Composition de résine photodurcissable
KR20090084340A (ko) 광경화형 수지 조성물 및 이를 이용한 수지 몰드의제조방법
KR101917156B1 (ko) 프린팅 프로세스용 광경화성 수지 조성물
WO2013095015A1 (fr) Procédé de fabrication de stratifié de film et stratifié de film formé selon ce procédé
CN110911273A (zh) 一种大面积图案化石墨烯的制备方法
WO2012086959A2 (fr) Composition de résine photodurcissable pour processus d'impression
WO2013019040A2 (fr) Composition de résine hybride organique-inorganique photodurcissable
WO2012102498A2 (fr) Composition de résine pouvant durcir par effet photochimique destinée à une lithographie d'impression
WO2017069431A1 (fr) Composition de résine photodurcissable et procédé de formation d'un motif l'utilisant
KR102130323B1 (ko) 기능성 물질을 이용한 패턴 필름의 제조방법 및 기능성 물질을 이용한 패턴 필름의 전사방법
WO2010041873A2 (fr) Procédé d'introduction dans des nanopores d'un précurseur de polymère par un effet de vide et procédé de duplication de précision de nanomotifs par ce procédé

Legal Events

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

Ref document number: 12814209

Country of ref document: EP

Kind code of ref document: A2

122 Ep: pct application non-entry in european phase

Ref document number: 12814209

Country of ref document: EP

Kind code of ref document: A2