WO2013161630A1 - 低離型力性を有するインプリント材料 - Google Patents
低離型力性を有するインプリント材料 Download PDFInfo
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- WO2013161630A1 WO2013161630A1 PCT/JP2013/061291 JP2013061291W WO2013161630A1 WO 2013161630 A1 WO2013161630 A1 WO 2013161630A1 JP 2013061291 W JP2013061291 W JP 2013061291W WO 2013161630 A1 WO2013161630 A1 WO 2013161630A1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 150000005075 thioxanthenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- 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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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- 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
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14625—Optical elements or arrangements associated with the device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to an imprint material (imprint film-forming composition) and a film produced from the material and having a pattern transferred thereto. More specifically, the present invention relates to an imprint material from which a resin film can be easily peeled off from a mold at the time of mold release after curing, and a film produced from the material and having a pattern transferred thereto.
- Nanoimprint lithography is a method in which a mold having an arbitrary pattern is brought into contact with a substrate on which a resin film is formed, the resin film is pressurized, and heat or light is used as an external stimulus to cure the target pattern.
- This nanoimprint lithography has an advantage that nanoscale processing can be performed easily and inexpensively as compared with optical lithography or the like in conventional semiconductor device manufacturing. Therefore, nanoimprint lithography is a technology that is expected to be applied to the manufacture of semiconductor devices, opto-devices, displays, storage media, biochips, etc., instead of optical lithography technology.
- Various reports have been made on curable compositions (Patent Documents 2 and 3).
- the force for peeling the mold from the cured resin film that is, the peeling force at the time of release (hereinafter referred to as “release” in this specification). If the mold force is abbreviated, the resin tends to adhere to the mold, making the mold unusable. For this reason, the material used for nanoimprint lithography (hereinafter abbreviated as “imprint material” in the present specification) is required to have low releasability (characteristic that allows the cured resin film to be easily peeled off from the mold). It becomes.
- the present invention has been made based on the above circumstances, and the problem to be solved is an imprint material that can easily peel off a resin film from a mold at the time of mold release after curing, that is, a low mold release. It is to provide an imprint material that forms a film having strength, high transparency, high scratch resistance, and high fingerprint wiping property, and a film produced from the material and having a pattern transferred thereon is provided. It is to be. Specifically, the release force is greater than 0 g / cm and 0.5 g / cm or less, the average transmittance in the visible light region is 99% or more, and the steel wool scratch test is performed on the film after transferring the pattern. An object of the present invention is to provide an imprint material that forms a film having 10 or less scratches when the above is performed.
- a material containing at least a propylene oxide unit and a polymerizable group, a silicone compound, and a photopolymerization initiator is an imprint material.
- the mold release is measured when the cured film in which the uneven pattern of the mold is transferred by photocuring of the material on the surface having the uneven shape of the mold is peeled off from the surface having the uneven shape of the mold.
- the force is remarkably small, and even when a film-transferred film made from the material is subjected to a steel wool scratch test on the pattern, there is little scratching, and it is excellent in fingerprint wiping and excellent in transparency.
- the present invention has been completed.
- this invention relates to the imprint material containing the following (A) component, (B) component, and (C) component as a 1st viewpoint.
- Component (A) A compound having a propylene oxide unit or a compound having a propylene oxide unit and an ethylene oxide unit and having two polymerizable groups
- B) component a silicone compound
- C) component a photopolymerization initiator
- the present invention relates to the imprint material according to the first aspect, further including a compound having three or more polymerizable groups as the component (D).
- a 3rd viewpoint it is related with the imprint material as described in a 1st viewpoint or a 2nd viewpoint which further contains the compound which has an ethylene oxide unit as a (E) component, and has two polymeric groups.
- a 4th viewpoint it is related with the imprint material as described in any one of a 1st viewpoint thru
- a 5th viewpoint it is related with the imprint material as described in any one of the 1st viewpoint thru
- the compound of the component (A) has at least two groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group as the polymerizable group.
- the compound of component (D) has three or more groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group as the polymerizable group.
- the imprint material according to the second aspect which is a compound.
- the imprint material is applied onto a film, the coating film on the film is adhered to a surface having a concavo-convex shape of a mold, the coating film is subsequently photocured, and then a cured film on the film
- the measured release force that is, the load when the cured film on the film is peeled from the surface having the concavo-convex shape of the mold
- the present invention relates to a film produced from the imprint material according to any one of the first to eighth aspects and having a pattern transferred thereto.
- a 10th viewpoint it is related with the optical member provided with the film
- an 11th viewpoint it is related with the solid-state imaging device provided with the film
- a 12th viewpoint it is related with the LED device provided with the film
- a 13th viewpoint it is related with the semiconductor element provided with the film
- a 14th viewpoint it is related with the solar cell provided with the film
- a 15th viewpoint it is related with the display provided with the film
- a 16th viewpoint it is related with the electronic device provided with the film
- the imprint material of the present invention contains a silicone compound together with a compound having a propylene oxide unit in the molecule or a compound having a propylene oxide unit and an ethylene oxide unit and having two polymerizable groups.
- the cured film produced from the imprint material has low release force, high scratch resistance, high fingerprint wiping property, and high transparency.
- the imprint material of the present invention can be photocured, and since a part of the pattern does not peel at the time of peeling from the surface having the uneven shape of the mold, a film in which a desired pattern is accurately formed is obtained. can get. Therefore, it is possible to form a good optical imprint pattern.
- the imprint material of the present invention can be formed on an arbitrary substrate, and a film to which a pattern formed after imprinting is transferred is scratch-resistant such as solar cells, LED devices, and displays. In addition, it can be suitably used for products that use members that require high fingerprint wiping and high transparency. Furthermore, the imprint material of this invention can control a cure rate, a dynamic viscosity, and a film thickness by changing the kind and content rate of the compound of the said (A) component. Therefore, the imprint material of the present invention can be designed suitably for the type of device to be manufactured, the type of exposure process and the type of baking process, and the process margin can be expanded. it can.
- the compound of the component (A) has one or more propylene oxide units or one or more propylene oxide units and one ethylene oxide unit in one molecule, and two polymerizable groups, specifically, It refers to a compound having a polymerizable group at both ends.
- the propylene oxide unit represents, for example, (—CH (CH 3 ) CH 2 O—) or (—CH 2 CH 2 CH 2 O—)
- the ethylene oxide unit represents, for example, (—CH 2 CH 2 O—).
- the polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
- the acryloyloxy group may be expressed as an acryloxy group
- the methacryloyloxy group may be expressed as a methacryloxy group.
- Examples of the compound as the component (A) include dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, and polypropylene glycol # 700 di (meth) acrylate. , Ethylene oxide propylene oxide copolymer di (meth) acrylic acid ester, and ethoxylated polypropylene glycol # 700 di (meth) acrylate.
- the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
- (meth) acrylic acid refers to acrylic acid and methacrylic acid.
- Economer A-1000PER above, Shin-Nakamura Chemical Co., Ltd.
- Funkrill registered trademark
- FA-P240A, FA-P270A, FA-023M above, Hitachi Chemical Co., Ltd.
- the compounds of the above component (A) can be used alone or in combination of two or more.
- the component (A) in the present invention can impart scratch resistance to the film after pattern transfer, and helps to bleed out the silicone compound of the component (B) described later at the time of curing during imprinting.
- the mold release force measured when the resin film (cured film) thus obtained is peeled from the surface having the uneven shape of the mold can be reduced.
- the dynamic viscosity of the imprint material, the curing speed at the time of imprint, and the film thickness to be formed can be controlled by changing the type and content ratio of the component (A).
- the silicone compound as component (B) represents a compound having a silicone skeleton (siloxane skeleton) in the molecule, and preferably has a dimethyl silicone skeleton.
- the above compounds are commercially available, and specific examples thereof include BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375. BYK-378, BYK-UV 3500, BYK-UV 3570 (manufactured by Big Chemie Japan Co., Ltd.), X-22-164, X-22-164AS, X-22-164A, X-22-164B, X -22-164C, X-22-164E, X-22-163, X-22-169AS, X-22-174DX, X-22-2426, X-22-9002, X-22-2475, X-22 -4952, KF-643, X-22-343, X-22-2404, X-22-2046, X-22-1602 Chemical Industry Co., Ltd.) and the like.
- the above compounds having a silicone skeleton can be used alone or in combination of two or more.
- the content of the component (B) in the imprint material of the present invention is the mass of the component (A) or the total mass of the component (A) and the component (D) when the component (D) described later is included.
- it is preferably 0.2 phr to 4 phr, more preferably 0.5 phr to 2 phr. If this ratio is less than 0.2 phr, sufficient low release force cannot be obtained, and if it exceeds 4 phr, curing may be insufficient and patterning characteristics deteriorate.
- phr represents the mass of the component (B) (silicone compound) with respect to 100 g of the mass of the component (A) or 100 g of the total mass of the components (A) and (D).
- the photopolymerization initiator as the component (C) is not particularly limited as long as it has absorption in the light source used at the time of photocuring.
- tert-butylperoxy-iso-butrate 2, 5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ ⁇ - (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2 , 5-bis (tert-butyldioxy) hexene hydroperoxide, ⁇ - (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5 -Trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) bar
- the above-mentioned compounds can be obtained as commercial products. Specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, Darocur (registered trademark) 1173, MBF, 4265, Lucirin (registered trademark) TPO (above, BASF) Japan Co., Ltd.), KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, Nippon Kayaku Co., Ltd.), VISURE-10, 55 (above, STAUFFER Co.
- IRGACURE registered trademark
- Darocur registered trademark
- ESACURE registered trademark
- KIP150, TZT 1001, KT 46, same KB1, same KL200, same KS300, same EB3, triazine-PMS, triazine A, triazine B (manufactured by Nippon Siebel Hegner), Adekaoptoma-N-1717, same N-1414, same N-1606 (stock) Company ADEKA).
- the above photopolymerization initiators can be used alone or in combination of two or more.
- the content of the component (C) in the imprint material of the present invention is the mass of the component (A) or the total mass of the component (A) and the component (D) when the component (D) described later is included.
- it is preferably 0.1 phr to 30 phr, more preferably 1 phr to 20 phr. This is because when the content ratio of the component (C) is less than 0.1 phr, sufficient curability cannot be obtained, and patterning characteristics are deteriorated and scratch resistance is deteriorated.
- phr represents the mass of the photopolymerization initiator with respect to 100 g of the mass of the component (A) or 100 g of the total mass of the components (A) and (D).
- a compound having three or more polymerizable groups may be added as the component (D).
- the compound having three or more polymerizable groups as component (D) plays a role of adjusting the hardness of the film obtained by photoimprinting.
- the number of polymerizable groups in the compound having three or more polymerizable groups is, for example, 3 to 6, and examples of the polymerizable group include acryloyloxy group, methacryloyloxy group, vinyl group, and allyl group. Can be mentioned.
- Examples of the compound (D) include pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, ethoxylated isocyanuric acid triacrylate, ⁇ - Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, dipentaerythritol poly Acrylate, polyglycerin polyethylene glycol polyacrylate, pentae Sri tall triacrylate hexamethylene diisocyanate urethane
- the compound having three or more polymerizable groups can be used alone or in combination of two or more.
- the proportion thereof is preferably 10 phr to 70 phr, more preferably 40 phr to 60 phr with respect to the mass of the component (A).
- a compound having an ethylene oxide unit and having two polymerizable groups may be added as the component (E). By further adding the component (E), it is possible to promote further reduction in the release force.
- the compound having an ethylene oxide unit as component (E) and having two polymerizable groups has one or more ethylene oxide units in one molecule and has two polymerizable groups, specifically It refers to a compound having a polymerizable group at both ends of the compound.
- the ethylene oxide unit represents, for example, (—CH 2 CH 2 O—).
- Examples of the polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
- Examples of the compound that is the component (E) include monoethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 300 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) acrylate, polyethylene glycol # 1000 di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate is mentioned.
- NK ester 1G, 2G, 3G, 4G, 9G, 14G, 23G, A-200, and A-400 include NK ester 1G, 2G, 3G, 4G, 9G, 14G, 23G, A-200, and A-400.
- the compound having the ethylene oxide unit and having two polymerizable groups can be used alone or in combination of two or more.
- the proportion thereof is 5% by mass or more in total with respect to the entire compound having a polymerizable group in the imprint material of the present invention. 35 mass% or less is preferable. If the total amount of the compound having a polymerizable group is less than 5% by mass, it hardly affects the reduction of the release force. Occurs and the shape deteriorates.
- a surfactant may be added as the component (F).
- the surfactant which is the component (F) plays a role of adjusting the film forming property of the obtained coating film.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such
- the above surfactants can be used alone or in combination of two or more.
- the ratio is the mass of the component (A), the total mass of the component (A) and the component (D), or the total mass of the component (A) and the component (E).
- it is preferably 0.01 phr to 40 phr, more preferably 0.01 phr to 10 phr with respect to the total mass of the component (A), the component (D) and the component (E).
- a solvent may be contained as the component (G).
- the solvent that is component (G) is a compound that contains propylene oxide units or propylene oxide units and ethylene oxide units in the molecule that is component (A) and has two polymerizable groups, and polymerizability that is component (D). It plays a role in adjusting the viscosity of a compound having three or more groups.
- solvent examples include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether.
- the said solvent can be used individually or in combination of 2 or more types.
- the solvent of the component (G) is removed from all the components of the imprint material of the present invention, that is, the components (A) to (F) described above, and all components including other additives described later.
- the proportion of the solid content defined as a thing contains the solvent in an amount of 20% by mass to 80% by mass, preferably 40% by mass to 60% by mass with respect to the imprint material. It is preferable.
- an epoxy compound As long as the imprint material of the present invention does not impair the effects of the present invention, an epoxy compound, a photoacid generator, a photosensitizer, an ultraviolet absorber, an antioxidant, an adhesion aid, or a mold release is used as necessary. A property improver can be contained.
- epoxy compound examples include Epolide (registered trademark) GT-401, PB3600, Celoxide (registered trademark) 2021P, 2000, 3000, EHPE3150, EHPE3150CE, Cyclomer (registered trademark) M100 (above, Inc.) Daicel), EPICLON (registered trademark) 840, 840-S, N-660, N-673-80M (above, manufactured by DIC Corporation).
- photoacid generator examples include IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (above, manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (Wako Pure Chemical Industries, Ltd.), TFE triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (Sanwa Chemical Co., Ltd.) Manufactured).
- IRGACURE registered trademark
- PAG103, PAG108, PAG121, PAG203, CGI725 above, manufactured by BASF Japan Ltd.
- WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 Wako Pure Chemical Industries, Ltd.
- TFE triazine TME-triazine
- photosensitizer examples include, for example, thioxanthene series, xanthene series, ketone series, thiopyrylium salt series, base styryl series, merocyanine series, 3-substituted coumarin series, 3,4-substituted coumarin series, cyanine series, acridine series. , Thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate.
- the above photosensitizers can be used alone or in combination of two or more.
- the absorption wavelength in the UV region can be adjusted by using the photosensitizer.
- UV absorber examples include TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, BASF Japan Ltd.).
- TINUVIN registered trademark
- PS 99-2, 109, 328, 384-2
- 400 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, BASF Japan Ltd.).
- the above ultraviolet absorbers can be used alone or in combination of two or more. By using the ultraviolet absorber, it is possible to control the curing speed of the outermost surface of the film during photocuring and to improve the mold release property.
- antioxidants examples include IRGANOX (registered trademark) 1010, 1035, 1076, 1135, 1520L (above, BASF Japan Ltd.).
- the above antioxidants can be used alone or in combination of two or more. By using the antioxidant, it is possible to prevent the film from turning yellow due to oxidation.
- adhesion aid examples include 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.
- the content of the adhesion aid is the mass of the component (A), the total mass of the component (A) and the component (D), the total mass of the component (A) and the component (E), or (A ) Component, (D) component, and (E) component, the amount is preferably 5 phr to 50 phr, more preferably 10 phr to 50 phr.
- Examples of the mold release improver include fluorine-containing compounds.
- Examples of the fluorine-containing compound include R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, and A-1630 (manufactured by Daikin Industries, Ltd.). It is done.
- the preparation method of the imprint material of this invention is not specifically limited, (D) component which is (A) component, (B) component, (C) component, and arbitrary components, (E) component, (F) component And the component (G) and other additives may be mixed as desired so that the imprint material is in a uniform state.
- the order of mixing the components (A) to (G) and other additives as desired is not particularly limited as long as a uniform imprint material can be obtained.
- Examples of the preparation method include a method in which the component (A) is mixed with the component (B) at a predetermined ratio.
- the imprint material of the present invention can be applied to a substrate and photocured to obtain a desired cured film.
- a coating method a known or well-known method such as a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, Examples thereof include brush coating, blade coating, and air knife coating.
- Examples of the base material to which the imprint material of the present invention is applied include silicon, glass on which indium tin oxide (ITO) is formed (hereinafter abbreviated as “ITO substrate” in this specification), silicon. Glass with nitride (SiN) film (SiN substrate), Glass with indium zinc oxide (IZO) film, polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, plastic, glass, quartz And a substrate made of ceramics or the like.
- ITO substrate in this specification
- SiN substrate Glass with nitride (SiN) film
- IZO indium zinc oxide
- PET polyethylene terephthalate
- TAC triacetyl cellulose
- flexible flexible substrates such as triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate. It is also possible to use a substrate made of phthalate, polyethersulfone, and a copolymer obtained by combining these polymers.
- the light source for curing the imprint material of the present invention is not particularly limited.
- the wavelength generally, a 436 nm G line, a 405 nm H line, a 365 nm I line, or a GHI mixed line can be used.
- the exposure dose is preferably 30 to 2000 mJ / cm 2 , more preferably 30 to 1000 mJ / cm 2 .
- the baking equipment is not particularly limited, and can be fired in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, or in a vacuum using, for example, a hot plate, an oven, or a furnace. If it is.
- the firing temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 ° C. to 200 ° C., for example.
- the optical imprinting apparatus is not particularly limited as long as a target pattern can be obtained.
- ST50 manufactured by Toshiba Machine Co., Ltd.
- Sindre registered trademark
- NM-0801HB manufactured by Meisho Kiko Co., Ltd.
- a commercially available device such as a device, a method in which a base material and a mold are pressure-bonded to a roller and released after photocuring can be used.
- examples of the mold material used for the optical imprint used in the present invention include quartz, silicon, nickel, alumina, carbonylsilane, and glassy carbon, but are not particularly limited as long as a target pattern can be obtained.
- the mold may be subjected to a mold release treatment for forming a thin film of a fluorine compound or the like on the surface thereof in order to improve the mold release property.
- examples of the mold release agent used for the mold release treatment include OPTOOL (registered trademark) HD and DSX manufactured by Daikin Industries, Ltd., but are not particularly limited as long as the target pattern can be obtained.
- the pattern size of the optical imprint is on the order of nanometers, specifically according to the pattern size of less than 1 micron.
- the 90 ° peel test for evaluating the release force is generally an adhesive (corresponding to a cured film formed from an imprint material in the present invention) and an adherend (corresponding to a film in the present invention). ) And is a test to measure the resistance (tension) generated when it is peeled in the 90 ° direction at a predetermined peeling speed after a predetermined time. Usually, the measurement is carried out by an evaluation method referring to JIS Z0237. The A value obtained by converting the resistance force measured here per width of the adherend can be evaluated as a release force.
- the imprint material of this invention was apply
- the value obtained by converting the load when completely peeled per 1 cm of the width of the film is preferably larger than 0 g / cm and not larger than 0.5 g / cm, more preferably not larger than 0.4 g / cm.
- a film produced from the imprint material of the present invention and having a pattern transferred thereon, a semiconductor element comprising the film, an optical member comprising the film on a substrate, a solid-state imaging device, an LED device, a solar cell, and a display And electronic devices are also the subject of the present invention.
- Example 1 5 g of NK ester APG-700 (hereinafter abbreviated as “APG-700” in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.05 g of BYK-333 (manufactured by Big Chemie Japan Ltd.) 1 phr) based on the mass of APG-700, and these were mixed, and the mixture was mixed with Lucirin (registered trademark) TPO (manufactured by BASF Japan Ltd.) (hereinafter abbreviated as “Lucirin TPO” in this specification). 0.125 g (2.5 phr based on the mass of APG-700) was added to prepare an imprint material PNI-a1.
- APG-700 NK ester APG-700
- Example 2 Example 1 except that APG-700 of Example 1 was changed to FANCLIL (registered trademark) FA-023M (hereinafter abbreviated as “FA-023M” in this specification) (manufactured by Hitachi Chemical Co., Ltd.). In the same manner as in Example 1, an imprint material PNI-a2 was prepared.
- FANCLIL registered trademark
- FA-023M registered trademark
- Example 3 Example 1 except that APG-700 in Example 1 was changed to NK Economer A-1000PER (hereinafter abbreviated as “A-1000PER” in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.). An imprint material PNI-a3 was prepared.
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- 0.5 g, UA-306H hereinafter referred to as “306H” in this specification
- 2 g produced by Kyoeisha Chemical Co., Ltd.
- 2.5 g of APG-700 2.5 g
- BYK-333 0.05 g
- Lucirin TPO 2.5 phr based on the total mass of DPEA-12, 306H and APG-700
- Example 5 An imprint material PNI-a5 was prepared in the same manner as in Example 4 except that BYK-333 of Example 4 was changed to 0.1 g (2 phr based on the total mass of DPEA-12, 306H, and APG-700). .
- Example 4 is the same as Example 4 except that APG-700 in Example 4 is changed to A-1000PER and BYK-333 is changed to 0.025 g (0.5 phr with respect to the total mass of DPEA-12, 306H and A-1000PER). Similarly, an imprint material PNI-a6 was prepared.
- Example 7 An imprint material PNI-a7 was prepared in the same manner as in Example 6 except that BYK-333 of Example 6 was changed to 0.05 g (1 phr with respect to the total mass of DPEA-12, 306H, and A-1000PER). .
- Example 8 An imprint material PNI-a8 was prepared in the same manner as in Example 6 except that BYK-333 of Example 6 was changed to 0.1 g (2 phr based on the total mass of DPEA-12, 306H, and A-1000PER). .
- Example 9 2.25 g of 306H and 2.75 g of A-1000PER were prepared and mixed. The mixture was mixed with 0.05 g of BYK-333 (1 phr based on the total mass of 306H and A-1000PER), and Lucirin TPO was 0. Imprint material PNI-a9 was prepared by adding .125 g (2.5 phr based on the total mass of 306H and A-1000PER).
- Example 10 1.25 g of DPEA-12, 1.25 g of KAYARAD (registered trademark) PET-30 (hereinafter abbreviated as “PET30” in this specification) (manufactured by Nippon Kayaku Co., Ltd.), and 2.1000 of A-1000PER. 5 g were prepared and mixed, and 0.1 g of BYK-333 (2 phr with respect to the total mass of DPEA-12, PET30 and A-1000PER) and 0.125 g of Lucirin TPO (DPEA-12, PET30) were mixed into the mixture. And 2.5 phr with respect to the total mass of A-1000PER) to prepare imprint material PNI-a10.
- PNI-a10 imprint material
- Example 11 2 g of PET30 and 3 g of A-1000PER were prepared and mixed. The mixture was mixed with 0.1 g of BYK-333 (2 phr based on the total mass of PET30 and A-1000PER) and 0.125 g of Lucirin TPO (PET30). And 2.5 phr) with respect to the total mass of A-1000PER) to prepare imprint material PNI-a11.
- NK Ester A-200 (hereinafter abbreviated as “A-200” in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5 g, A-1000PER 3 g, DPEA-12 0.5 g These were mixed, and 0.05 g of BYK-333 (1 phr based on the total mass of A-200, A-1000PER and DPEA-12) and 0.125 g of Lucirin TPO (A200, A-1000PER) were mixed into the mixture. And 2.5 phr with respect to the total mass of DPEA-12) to prepare imprint material PNI-a12.
- Example 13 Prepare 1.5 g of A-200, 2.5 g of A-1000PER, and 1 g of DPEA-12, mix them, and add 0.05 g of BYK-333 to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a13 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 14 Prepare 1.5 g of A-200, 2 g of A-1000PER and 1.5 g of DPEA-12, mix them, and add 0.05 g of BYK-333 to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a14 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 15 Prepare 1.5 g of A-200, 1.5 g of A-1000PER, and 2 g of DPEA-12, mix them, and add 0.05 g of BYK-333 to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a15 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 16 Prepare 1.5 g of A-200, 1 g of A-1000PER, and 2.5 g of DPEA-12, mix them, and add 0.05 g of BYK-333 to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a16 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 17 Prepare 1.5 g of A-200, 0.5 g of A-1000PER, and 3 g of DPEA-12, mix them, and add 0.05 g of BYK-333 to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a17 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 18 1 g of A-200, 1.5 g of A-1000PER, and 2.5 g of DPEA-12 were prepared and mixed, and 0.05 g of BYK-333 was added to the mixture (A-200, A-1000PER and DPEA- Imprint material PNI-a18 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- Example 19 1 g of A-200, 1 g of A-1000PER, and 3 g of DPEA-12 were prepared and mixed, and 0.05 g of BYK-333 was added to the mixture (the total mass of A-200, A-1000PER and DPEA-12).
- the imprint material PNI-a19 was prepared by adding 0.125 g of Lucirin TPO (2.5 phr with respect to the total mass of A200, A-1000PER and DPEA-12).
- ⁇ Comparative Example 1> Prepare 5 g of 306H, 0.05 g of BYK-333 (1 phr for the mass of 306H), 0.125 g of Lucirin TPO (2.5 phr for the mass of 306H), mix them, and imprint material PNI -B1 was prepared.
- ⁇ Comparative Example 5> Prepare 0.5 g of DPEA-12, 2 g of 306H and 2.5 g of APG-700, mix them, and add 0.125 g of Lucirin TPO to the total mass of DPEA-12, 306H and APG-700. 2.5 phr) was added to prepare an imprint material PNI-b5.
- Each imprint material obtained in Example 1 to Example 19 and Comparative Example 1 to Comparative Example 6 was prepared by using a triacetyl cellulose film having a thickness of 80 ⁇ m (using Fujitac (registered trademark) manufactured by Fuji Film Co., Ltd.) In this specification, it is abbreviated as “TAC film”) using a bar coater (fully automated film applicator KT-AB3120 manufactured by Co-Tech Co., Ltd.), and the coating film on the TAC film is subjected to the above-described release treatment. Roller pressure bonding was applied to the applied moth-eye pattern mold.
- the coating film was exposed to light at 350 mJ / cm 2 from the TAC film side with an electrodeless uniform irradiation apparatus (QRE-4016A, manufactured by Oak Manufacturing Co., Ltd.), and photocured. Then, a 90 ° peel test was performed with reference to JIS Z0237, and the cured film formed on the TAC film adhered to the surface having the uneven shape of the mold was completely peeled from the surface having the uneven shape of the mold. When the load was measured. The load per 1 cm width of the film was calculated and used as the release force (g / cm). The results are shown in Table 1.
- Step wool scratch test A steel wool scratch test was performed on the cured film obtained after the release force test.
- the test machine used was made by Daiei Seiki Co., Ltd., and # 0000 steel wool was used.
- the load per unit area was 20.4 g / cm 2 and the steel wool was reciprocated 10 times.
- the number of scratches after abrasion was evaluated as follows. The results are shown in Table 1. 0 to 5: A 6-10: B 11-20: C 21-30: D 31 to 40: E
- Example 1 to Example 8 and Example 12 to Example 19 Each imprint material obtained in Example 1 to Example 8 and Example 12 to Example 19 was used on a TAC film having a thickness of 80 ⁇ m using a bar coater (fully automatic film applicator KT-AB3120 manufactured by Cortec Co., Ltd.). Then, the coating film on the TAC film was roller-bonded to the moth-eye pattern mold subjected to the above-described release treatment. Subsequently, the coating film was exposed to light at 350 mJ / cm 2 from the TAC film side with an electrodeless uniform irradiation apparatus (QRE-4016A, manufactured by Oak Manufacturing Co., Ltd.), and photocured.
- QRE-4016A an electrodeless uniform irradiation apparatus
- the surface of the TAC film opposite to the surface on which the cured film having the transferred moth-eye pattern was formed was painted black with Super Lacquer Spray (manufactured by Asahi Pen Co., Ltd.). Then, an artificial fingerprint liquid (manufactured by TDK Co., Ltd.) was adhered onto the moth-eye pattern of the cured film formed on the TAC film, and Bencot (registered trademark) M-1 (Asahi Kasei) was used in the test machine used in the steel wool scratch test.
- a fingerprint wiping test was performed by reciprocating 50 times with a load of 570 g / cm 2 , and the wiping property of the fingerprint was visually confirmed.
- the wipe performed in the test is a dry wipe. Table 2 shows the results of evaluation of “ ⁇ ” when the fingerprint could be wiped after the wiping test, and “X” when the fingerprint could not be wiped, that is, when the fingerprint remained.
- the release force was as low as 0.5 g / cm or less in all cases, and the obtained cured film was in the visible light region. It had high transparency, and the number of scratches generated after the steel wool scratch test was small, and scratch resistance was confirmed.
- the release force was much larger than 0.5 g / cm, and many scratches were generated after the steel wool scratch test. From the results of Table 2, it was confirmed that fingerprints can be wiped off when using the imprint materials obtained in Examples 1 to 8 and Examples 12 to 19. .
- the film obtained from the imprint material of the present invention has low release power, excellent scratch resistance and fingerprint wiping after imprinting, and excellent transparency. .
- the imprint material of the present invention can easily peel a cured film formed from the material from the mold, and also has excellent scratch resistance, fingerprint wiping property, and transparency.
- the obtained cured film can be suitably used for products such as solar cells, LED devices, and displays.
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Abstract
Description
したがって、ナノインプリントリソグラフィは、光リソグラフィ技術に代わり、半導体デバイス、オプトデバイス、ディスプレイ、記憶媒体、バイオチップ等の製造への適用が期待されている技術であることから、ナノインプリントリソグラフィに用いる光ナノインプリントリソグラフィ用硬化性組成物について様々な報告がなされている(特許文献2、特許文献3)。
(A)成分:プロピレンオキサイドユニットを有し又はプロピレンオキサイドユニット及びエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物
(B)成分:シリコーン化合物
(C)成分:光重合開始剤
第2観点として、(D)成分として重合性基を3つ以上有する化合物をさらに含有する、第1観点に記載のインプリント材料に関する。
第3観点として、(E)成分としてエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物をさらに含有する、第1観点又は第2観点に記載のインプリント材料に関する。
第4観点として、(F)成分として界面活性剤をさらに含有する、第1観点乃至第3観点のいずれか一つに記載のインプリント材料に関する。
第5観点として、(G)成分として溶剤をさらに含有する、第1観点乃至第4観点のいずれか一つに記載のインプリント材料に関する。
第6観点として、前記(A)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を2つ有する化合物である、第1観点乃至第5観点のいずれか一つに記載のインプリント材料に関する。
第7観点として、前記(D)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を3つ以上有する化合物である、第2観点に記載のインプリント材料に関する。
第8観点として、前記インプリント材料をフィルム上に塗布し、該フィルム上の塗膜をモールドの凹凸形状を有する面に接着させ、続いて該塗膜を光硬化させ、その後フィルム上の硬化膜をモールドの凹凸形状を有する面から90°剥離する試験において、計測された離型力、すなわち、該フィルム上の硬化膜をモールドの凹凸形状を有する面から剥離したときの荷重を該フィルムの横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下である、第1観点乃至第7観点のいずれか一つに記載のインプリント材料に関する。
第9観点として、第1観点乃至第8観点のうちいずれか一つに記載のインプリント材料から作製され、パターンが転写された膜に関する。
第10観点として、第9観点に記載のパターンが転写された膜を基材上に備えた光学部材に関する。
第11観点として、第9観点に記載のパターンが転写された膜を基材上に備えた固体撮像装置に関する。
第12観点として、第9観点に記載のパターンが転写された膜を基材上に備えたLEDデバイスに関する。
第13観点として、第9観点に記載のパターンが転写された膜を備えた半導体素子に関する。
第14観点として、第9観点に記載のパターンが転写された膜を基材上に備えた太陽電池に関する。
第15観点として、第9観点に記載のパターンが転写された膜を基材上に備えたディスプレイに関する。
第16観点として、第9観点に記載のパターンが転写された膜を基材上に備えた電子デバイスに関する。
また本発明のインプリント材料は、光硬化が可能であり、かつモールドの凹凸形状を有する面からの剥離時にパターンの一部に剥がれが生じないため、所望のパターンが正確に形成された膜が得られる。したがって、良好な光インプリントのパターン形成が可能である。
また、本発明のインプリント材料は、任意の基材上に製膜することができ、インプリント後に形成されるパターンが転写された膜は、太陽電池、LEDデバイス、ディスプレイなどの、耐擦傷性、高指紋拭き取り性及び高透明性が求められる部材を使用する製品へ好適に用いることができる。
さらに、本発明のインプリント材料は、上記(A)成分の化合物の種類及び含有割合を変更することで、硬化速度、動的粘度、膜厚をコントロールすることができる。したがって、本発明のインプリント材料は、製造するデバイス種と露光プロセス及び焼成プロセスの種類に対応した材料の設計が可能であり、プロセスマージンを拡大できるため、光学部材の製造に好適に用いることができる。
(A)成分の化合物は、一分子内にプロピレンオキサイドユニットを1つ以上、又はプロピレンオキサイドユニット及びエチレンオキサイドユニットをそれぞれ1つ以上有し、かつ重合性基を2つ、具体的には化合物の両末端に重合性基を有する化合物を指す。なお、上記プロピレンオキサイドユニットとは例えば(-CH(CH3)CH2O-)、(-CH2CH2CH2O-)を表し、上記エチレンオキサイドユニットとは例えば(-CH2CH2O-)を表す。また当該重合性基としては、例えば、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基、アリル基が挙げられる。ここで、アクリロイルオキシ基はアクリロキシ基と、メタアクリロイルオキシ基はメタアクリロキシ基と表現されることがある。
また上記(A)成分の化合物の種類及び含有割合を変更することで、インプリント材料の動的粘度、インプリント時の硬化速度及び形成される膜厚をコントロールすることができる。
(B)成分であるシリコーン化合物は、分子内にシリコーン骨格(シロキサン骨格)を有する化合物を表し、特にジメチルシリコーン骨格を有することが好ましい。
(C)成分である光重合開始剤としては、光硬化時に使用する光源に吸収をもつものであれば、特に限定されるものではないが、例えば、tert-ブチルペルオキシ-iso-ブタレート、2,5-ジメチル-2,5-ビス(ベンゾイルジオキシ)ヘキサン、1,4-ビス[α-(tert-ブチルジオキシ)-iso-プロポキシ]ベンゼン、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ビス(tert-ブチルジオキシ)ヘキセンヒドロペルオキシド、α-(iso-プロピルフェニル)-iso-プロピルヒドロペルオキシド、tert-ブチルヒドロペルオキシド、1,1-ビス(tert-ブチルジオキシ)-3,3,5-トリメチルシクロヘキサン、ブチル-4,4-ビス(tert-ブチルジオキシ)バレレート、シクロヘキサノンペルオキシド、2,2’,5,5’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-アミルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3’-ビス(tert-ブチルペルオキシカルボニル)-4,4’-ジカルボキシベンゾフェノン、tert-ブチルペルオキシベンゾエート、ジ-tert-ブチルジペルオキシイソフタレート等の有機過酸化物;9,10-アントラキノン、1-クロロアントラキノン、2-クロロアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン等のキノン類;ベンゾインメチル、ベンゾインエチルエーテル、α-メチルベンゾイン、α-フェニルベンゾイン等のベンゾイン誘導体;2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-[4-{4-(2-ヒドロキシ-2-メチル-プロピオニル)ベンジル}-フェニル]-2-メチル-プロパン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、2-ジメチルアミノ-2-(4-メチル-ベンジル)-1-(4-モルホリン-4-イル-フェニル)-ブタン-1-オン等のアルキルフェノン系化合物;ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド等のアシルホスフィンオキサイド系化合物;1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)等のオキシムエステル系化合物が挙げられる。
本発明においては(D)成分として重合性基を3つ以上有する化合物を添加してもよい。(D)成分である重合性基を3つ以上有する化合物は光インプリントにより得られる膜の硬度を調整する役割を果たす。重合性基を3つ以上有する化合物の重合性基の数は、例えば3つ乃至6つであり、当該重合性基としては、例えば、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基、アリル基が挙げられる。
本発明においては(E)成分としてエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物を添加してもよい。(E)成分を添加することでより一層の離型力の低下を促進することが可能である。(E)成分であるエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物は、一分子内にエチレンオキサイドユニットを1つ以上有し、かつ重合性基を2つ、具体的には化合物の両末端に重合性基を有する化合物を指す。なお、上記エチレンオキサイドユニットとは例えば(-CH2CH2O-)を表す。また当該重合性基としては、例えば、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基、アリル基が挙げられる。
本発明においては(F)成分として界面活性剤を添加してもよい。(F)成分である界面活性剤は、得られる塗膜の製膜性を調整する役割を果たす。
上記界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤;商品名エフトップ(登録商標)EF301、同EF303、同EF352(三菱マテリアル電子化成株式会社(旧株式会社ジェムコ製))、商品名メガファック(登録商標)F171、同F173、同R-08、同R-30(DIC株式会社製)、フロラードFC430、同FC431(住友スリーエム株式会社製)、商品名アサヒガード(登録商標)AG710、サーフロン(登録商標)S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子株式会社製)等のフッ素系界面活性剤;及びオルガノシロキサンポリマーKP341(信越化学工業株式会社製)を挙げることができる。
本発明においては(G)成分として溶剤を含有してもよい。(G)成分である溶剤は、(A)成分である分子中にプロピレンオキサイドユニット又はプロピレンオキサイドユニットとエチレンオキサイドユニットを含有し、重合性基を2つ有する化合物及び(D)成分である重合性基を3つ以上有する化合物の粘度調節の役割を果たす。
溶剤が使用される場合、本発明のインプリント材料の全成分、すなわち前述の(A)成分乃至(F)成分、並びに後述するその他添加剤を含む全成分から(G)成分の溶剤を除いたものとして定義される固形分の割合が、前記インプリント材料に対して20質量%乃至80質量%となる量にて、好ましくは40質量%乃至60質量%となる量にて、溶剤を含有することが好ましい。
本発明のインプリント材料は、本発明の効果を損なわない限りにおいて、必要に応じて、エポキシ化合物、光酸発生剤、光増感剤、紫外線吸収剤、酸化防止剤、密着補助剤又は離型性向上剤を含有することができる。
本発明のインプリント材料の調製方法は、特に限定されないが、(A)成分、(B)成分、(C)成分、並びに任意成分である(D)成分、(E)成分、(F)成分及び(G)成分並びに所望によりその他添加剤を混合し、インプリント材料が均一な状態となっていればよい。
また、(A)成分乃至(G)成分並びに所望によりその他添加剤を混合する際の順序は、均一なインプリント材料が得られるなら問題なく、特に限定されない。当該調製方法としては、例えば、(A)成分に(B)成分を所定の割合で混合する方法が挙げられる。また、これに更に(C)成分、(D)成分、(E)成分、(F)成分及び(G)成分を混合し、均一なインプリント材料とする方法も挙げられる。さらに、この調製方法の適当な段階において、必要に応じて、その他の添加剤を更に添加して混合する方法が挙げられる。
本発明のインプリント材料は、基材上に塗布し光硬化させることで所望の硬化膜を得ることができる。塗布方法としては、公知又は周知の方法、例えば、スピンコート法、ディップ法、フローコート法、インクジェット法、スプレー法、バーコート法、グラビアコート法、スリットコート法、ロールコート法、転写印刷法、刷毛塗り、ブレードコート法、エアーナイフコート法を挙げることができる。
そして本発明のインプリント材料をフィルム上に塗布し、該フィルム上の塗膜をモールドの凹凸形状を有する面に接着させ、続いて該塗膜を、モールドの凹凸形状を有する面を接着させたまま光硬化させ、その後フィルム上の硬化膜をモールドの凹凸形状を有する面から90°剥離する試験において計測された離型力、すなわち、該フィルム上の硬化膜をモールドの凹凸形状を有する面から完全に剥離したときの荷重を該フィルムの横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下であることが好ましく、より好ましくは0.4g/cm以下である。
<実施例1>
NKエステル APG-700(以下、本明細書では「APG-700」と略称する。)(新中村化学工業株式会社製)を5g、BYK-333(ビックケミー・ジャパン株式会社製)を0.05g(APG-700の質量に対して1phr)準備し、これらを混合し、その混合物にLucirin(登録商標)TPO(BASFジャパン株式会社製)(以下、本明細書では「Lucirin TPO」と略称する。)を0.125g(APG-700の質量に対して2.5phr)加え、インプリント材料PNI-a1を調製した。
実施例1のAPG-700をファンクリル(登録商標)FA-023M(以下、本明細書では「FA-023M」と略称する。)(日立化成工業株式会社製)へ変更した以外は、実施例1と同様にインプリント材料PNI-a2を調製した。
実施例1のAPG-700をNKエコノマー A-1000PER(以下、本明細書では「A-1000PER」と略称する。)(新中村化学工業株式会社製)へ変更した以外は、実施例1と同様にインプリント材料PNI-a3を調製した。
KAYARAD(登録商標)DPEA-12(以下、本明細書では「DPEA-12」と略称する。)(日本化薬株式会社製)を0.5g、UA-306H(以下、本明細書では「306H」と略称する。)(共栄社化学株式会社製)を2g、APG-700を2.5g、BYK-333を0.05g(DPEA-12、306H及びAPG-700の総質量に対して1phr)準備し、これらを混合し、その混合物にLucirin TPOを0.125g(DPEA-12、306H及びAPG-700の総質量に対して2.5phr)加え、インプリント材料PNI-a4を調製した。
実施例4のBYK-333を0.1g(DPEA-12、306H及びAPG-700の総質量に対して2phr)へ変更した以外は、実施例4と同様にインプリント材料PNI-a5を調製した。
実施例4のAPG-700をA-1000PERへ、BYK-333を0.025g(DPEA-12、306H及びA-1000PERの総質量に対して0.5phr)へ変更した以外は、実施例4と同様にインプリント材料PNI-a6を調製した。
実施例6のBYK-333を0.05g(DPEA-12、306H及びA-1000PERの総質量に対して1phr)へ変更した以外は、実施例6と同様にインプリント材料PNI-a7を調製した。
実施例6のBYK-333を0.1g(DPEA-12、306H及びA-1000PERの総質量に対して2phr)へ変更した以外は、実施例6と同様にインプリント材料PNI-a8を調製した。
306Hを2.25gとA-1000PERを2.75g準備し、これらを混合し、その混合物にBYK-333を0.05g(306H及びA-1000PERの総質量に対して1phr)、Lucirin TPOを0.125g(306HとA-1000PERの総質量に対して2.5phr)加えてインプリント材料PNI-a9を調製した。
DPEA-12を1.25g、KAYARAD(登録商標)PET-30(以下、本明細書では「PET30」と略称する。)(日本化薬株式会社製)を1.25g、A-1000PERを2.5g準備し、これらを混合し、その混合物にBYK-333を0.1g(DPEA-12、PET30及びA-1000PERの総質量に対して2phr)、Lucirin TPOを0.125g(DPEA-12、PET30及びA-1000PERの総質量に対して2.5phr)加え、インプリント材料PNI-a10を調製した。
PET30を2g、A-1000PERを3g準備し、これらを混合し、その混合物にBYK-333を0.1g(PET30及びA-1000PERの総質量に対して2phr)、Lucirin TPOを0.125g(PET30及びA-1000PERの総質量に対して2.5phr)加え、インプリント材料PNI-a11を調製した。
NKエステル A-200(以下、本明細書では「A-200」と略称する。)(新中村化学工業株式会社製)を1.5g、A-1000PERを3g、DPEA-12を0.5g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a12を調製した。
A-200を1.5g、A-1000PERを2.5g、DPEA-12を1g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a13を調製した。
A-200を1.5g、A-1000PERを2g、DPEA-12を1.5g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a14を調製した。
A-200を1.5g、A-1000PERを1.5g、DPEA-12を2g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a15を調製した。
A-200を1.5g、A-1000PERを1g、DPEA-12を2.5g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a16を調製した。
A-200を1.5g、A-1000PERを0.5g、DPEA-12を3g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a17を調製した。
A-200を1g、A-1000PERを1.5g、DPEA-12を2.5g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a18を調製した。
A-200を1g、A-1000PERを1g、DPEA-12を3g準備し、これらを混合し、その混合物にBYK-333を0.05g(A-200、A-1000PER及びDPEA-12の総質量に対して1phr)、Lucirin TPOを0.125g(A200、A-1000PER及びDPEA-12の総質量に対して2.5phr)加え、インプリント材料PNI-a19を調製した。
306Hを5g、BYK-333を0.05g(306Hの質量に対して1phr)、Lucirin TPOを0.125g(306Hの質量に対して2.5phr)準備し、これらを混合し、インプリント材料PNI-b1を調製した。
比較例1のBYK-333を0.1g(306Hの質量に対して2phr)へ変更した以外は、比較例1と同様にインプリント材料PNI-b2を調製した。
比較例1の306HをPET30へ変更した以外は、比較例1と同様にインプリント材料PNI-b3を調製した。
比較例2の306HをPET30へ変更した以外は、比較例2と同様にインプリント材料PNI-b4を調製した。
DPEA-12を0.5g、306Hを2g、APG-700を2.5g準備し、これらを混合し、その混合物にLucirin TPOを0.125g(DPEA-12、306HとAPG-700の総質量に対して2.5phr)加え、インプリント材料PNI-b5を調製した。
比較例5のAPG700をA-1000PERへ変更した以外は、比較例5と同様にインプリント材料PNI-b6を調製した。
ニッケル製のピッチ250nm、高さ250nmのモスアイパターンモールド(株式会社イノックス製)及びシリコンウエハを、オプツール(登録商標)DSX(ダイキン工業株式会社製)をノベック(登録商標)HFE-7100(ハイドロフルオロエーテル、住友スリーエム株式会社)(以下、本明細書では「ノベックHFE-7100」と略称する。)で0.1質量%に希釈した溶液へ浸漬し、温度が90℃、湿度が90RH%の高温高湿装置を用いて1時間処理し、ノベックHFE-7100でリンス後、エアーで乾燥させた。
実施例1乃至実施例19及び比較例1乃至比較例6で得られた各インプリント材料を、厚さ80μmのトリアセチルセルロースフィルム(富士フイルム株式会社製 フジタック(登録商標)を使用)(以下、本明細書では「TACフィルム」と略称する。)上にバーコーター(全自動フィルムアプリケーター KT-AB3120 コーテック株式会社製)を用いて塗布し、そのTACフィルム上の塗膜を前述の離型処理を施したモスアイパターンモールドへローラー圧着させた。続いて該塗膜に対し、TACフィルム側から無電極均一照射装置(QRE-4016A、株式会社オーク製作所製)にて、350mJ/cm2の露光を施し、光硬化を行った。そしてJIS Z0237を参考にして90°剥離試験を行い、モールドの凹凸形状を有する面と接着している、TACフィルム上に形成された硬化膜が、モールドの凹凸形状を有する面から完全に剥がれたときの荷重を測定した。そしてフィルムの幅1cm当たりの荷重を算出し、離型力(g/cm)とした。結果を表1に示す。
上記離型力試験後に得られた硬化膜について、スチールウール擦傷試験を行った。試験機は大栄精機(有)製を使用し、♯0000のスチールウールを使用した。単位面積当たりの荷重は20.4g/cm2とし、上記スチールウールを10往復させた。擦傷後の傷本数については以下のように評価した。結果を表1に示す。
0~ 5本:A
6~10本:B
11~20本:C
21~30本:D
31~40本:E
実施例1乃至実施例19及び比較例1乃至比較例6で得られた各インプリント材料を石英基板上にスピンコートし、前述の離型処理をしたシリコンウエハを接着させ、ナノインプリント装置(NM-0801HB、明昌機工株式会社製)に設置し、10秒間かけて100Nまで加圧して膜中の気泡を除去し、10秒間かけて除圧した後、無電極均一照射装置にて、350mJ/cm2の露光を施した。そしてシリコンウエハを剥がし、石英基板上に作製した厚さ5μmの膜について、透過率測定を行った。試験機としてSHIMADSU UV-3600(株式会社島津製作所製)を用いて、可視光領域における平均透過率を調べた。得られた結果を表1に示す。
実施例1乃至実施例8及び実施例12乃至実施例19で得られた各インプリント材料を、厚さ80μmのTACフィルム上にバーコーター(全自動フィルムアプリケーター KT-AB3120 コーテック株式会社製)を用いて塗布し、そのTACフィルム上の塗膜を前述の離型処理を施したモスアイパターンモールドへローラー圧着させた。続いて該塗膜に対し、TACフィルム側から無電極均一照射装置(QRE-4016A、株式会社オーク製作所製)にて、350mJ/cm2の露光を施し、光硬化を行った。モールドから離型後、上記TACフィルムにおいてモスアイパターンが転写された硬化膜が形成された面とは反対の面をスーパーラッカースプレー(アサヒペン株式会社製)にて黒色に塗装した。そして、TACフィルム上に形成された硬化膜のモスアイパターン上に人工指紋液(TDK株式会社製)を付着させ、上記スチールウール擦傷試験で用いた試験機にベンコット(登録商標)M-1(旭化成せんい株式会社製)を取り付け、570g/cm2の荷重にて50往復させる指紋の拭き取り試験を行い、目視にて指紋の拭き取り性を確認した。当該試験で行われる拭き取りは乾拭きである。拭き取り試験後、指紋の拭き取りができた場合を○、指紋の拭き取りができなかった即ち指紋が残存していた場合を×と評価した結果を、表2に示す。
以上、本発明のインプリント材料により得られる膜は、低離型力性を有し、またインプリント後も優れた耐擦傷性及び指紋の拭き取り性を有し、しかも透明性に優れるものとなる。
Claims (16)
- 下記(A)成分、(B)成分及び(C)成分を含有するインプリント材料。
(A)成分:プロピレンオキサイドユニットを有し又はプロピレンオキサイドユニット及びエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物
(B)成分:シリコーン化合物
(C)成分:光重合開始剤 - (D)成分として重合性基を3つ以上有する化合物をさらに含有する、請求項1に記載のインプリント材料。
- (E)成分としてエチレンオキサイドユニットを有し、かつ重合性基を2つ有する化合物をさらに含有する、請求項1又は請求項2に記載のインプリント材料。
- (F)成分として界面活性剤をさらに含有する、請求項1乃至請求項3のいずれか一項に記載のインプリント材料。
- (G)成分として溶剤をさらに含有する、請求項1乃至請求項4のいずれか一項に記載のインプリント材料。
- 前記(A)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を2つ有する化合物である、請求項1乃至請求項5のいずれか一項に記載のインプリント材料。
- 前記(D)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を3つ以上有する化合物である、請求項2に記載のインプリント材料。
- 前記インプリント材料をフィルム上に塗布し、該フィルム上の塗膜をモールドの凹凸形状を有する面に接着させ、続いて該塗膜を光硬化させ、その後フィルム上の硬化膜をモールドの凹凸形状を有する面から90°剥離する試験において、計測された離型力、すなわち、該フィルム上の硬化膜をモールドの凹凸形状を有する面から剥離したときの荷重を該フィルムの横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下である、請求項1乃至請求項7のいずれか一項に記載のインプリント材料。
- 請求項1乃至請求項8のうちいずれか一項に記載のインプリント材料から作製され、パターンが転写された膜。
- 請求項9に記載のパターンが転写された膜を基材上に備えた光学部材。
- 請求項9に記載のパターンが転写された膜を基材上に備えた固体撮像装置。
- 請求項9に記載のパターンが転写された膜を基材上に備えたLEDデバイス。
- 請求項9に記載のパターンが転写された膜を備えた半導体素子。
- 請求項9に記載のパターンが転写された膜を基材上に備えた太陽電池。
- 請求項9に記載のパターンが転写された膜を基材上に備えたディスプレイ。
- 請求項9に記載のパターンが転写された膜を基材上に備えた電子デバイス。
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