US20100019410A1 - Resin for Thermal Imprinting - Google Patents
Resin for Thermal Imprinting Download PDFInfo
- Publication number
- US20100019410A1 US20100019410A1 US12/086,165 US8616506A US2010019410A1 US 20100019410 A1 US20100019410 A1 US 20100019410A1 US 8616506 A US8616506 A US 8616506A US 2010019410 A1 US2010019410 A1 US 2010019410A1
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- US
- United States
- Prior art keywords
- mold
- resin
- film
- thermal imprint
- pattern
- 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.)
- Abandoned
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- 0 [1*]C1(C)C([2*])(C)C2([4*])C([5*])([6*])C1([3*])C1([7*])C2([8*])C([9*])C2([11*])C1([10*])C1([12*])C([14*])([15*])C2([13*])C([18*])([19*])C1([16*])[17*].[20*]C(C)C1([24*])C([22*])([23*])C([25*])(C([21*])C)C([26*])([27*])C1([28*])[29*] Chemical compound [1*]C1(C)C([2*])(C)C2([4*])C([5*])([6*])C1([3*])C1([7*])C2([8*])C([9*])C2([11*])C1([10*])C1([12*])C([14*])([15*])C2([13*])C([18*])([19*])C1([16*])[17*].[20*]C(C)C1([24*])C([22*])([23*])C([25*])(C([21*])C)C([26*])([27*])C1([28*])[29*] 0.000 description 15
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/005—Surface shaping of articles, e.g. embossing; Apparatus therefor characterised by the choice of material
-
- 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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2045/00—Use of polymers of unsaturated cyclic compounds having no unsaturated aliphatic groups in a side-chain, e.g. coumarone-indene resins or derivatives thereof, as moulding material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/0108—Male die used for patterning, punching or transferring
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0014—Shaping of the substrate, e.g. by moulding
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material
Definitions
- the present invention relates to a resin for thermal imprint. More specifically, the present invention relates to a cyclic-olefin-based thermoplastic resin which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., and can be used for producing a sheet or a film.
- Tg glass transition temperature
- Injection molding has its limitation below 500 ⁇ m of film thickness.
- various advanced devices including anti reflecting film or coating requires patterning on a sheet or a film with thickness much below the limit of injection molding.
- a thermal imprint method for forming a minute pattern at low cost is a method of pressing a mold, having a minute pattern heated more than or equal to a glass transition temperature of a resin, against a resin substrate, and of transferring the minute pattern of the mold on the melted resin surface.
- examples of materials used for thermal imprint are resin materials, glasses, metals, and the like.
- the resin materials can be molded at a lower temperature in comparison with imprinting to metals or glasses, thus advantageous for the manufacturing cost.
- resins is a (meta) acrylic resin represented by polymethacrylic acid (PMMA) or a polycarbonate resin, but have a problem such that the heat resistance is low and size distortion occurs due to water absorption. Further, controlling a balance between the fluidity and the solidification is difficult, so that it is difficult to maintain and use a minutely-transferred pattern (see, for example, patent literature 3).
- cyclic-olefin-based thermoplastic resins As a resin having both heat resistance and dimension stability originating from the low water absorption coefficient, there are cyclic-olefin-based thermoplastic resins.
- the cyclic-olefin-based thermoplastic resins are superior in the transparency, the chemical resistance property, and the low moisture absorption characteristic, and its heat resistance can be easily controlled by the structure of the cyclic-olefin or the contained amount of the cyclic-olefin in the resin.
- the resin has a low viscosity, and a short relaxation time (time necessary for filling the resin in the pattern of a mold), and is less adhered to the mold, and is superior in the transfer accuracy of a minute pattern, so that application as a thermal imprint material is expected as having a good productivity (see, for example, non-patent literature 1).
- Patent Literature 1 Japanese Unexamined Patent Application Laid-open Publication No.2002-361500
- Patent Literature 2 Japanese Unexamined Patent Application Laid-open Publication No.2004-288811
- Patent Literature 3 Japanese Unexamined Patent Application Laid-open Publication No. 2000-158532
- Non-patent Literature 1 J. Mater. Chem., 2000, volume 10, page 2634
- Non-patent Literature 2 Nanoimprint Lithography in Topas, a highly UV-transparent and chemically resistant thrmoplast, T. Nielsen, D. Nilsson, et al.
- thermoplastic resins are not ones that the resin properties, such as a glass transition temperature Tg (° C.) and the fluidity are developed for the process of thermal nano-imprint, but require a high molding temperature and a large molding pressure, thus having insufficient thermal imprint characteristics (transferability, mold release characteristic, and the like). Moreover, a long molding time is required, so that the productivity (throughput) is low.
- Tg glass transition temperature
- a long molding time is required, so that the productivity (throughput) is low.
- one disclosed in the foregoing non-patent literature 1 has a high molding temperature of 240° C., so that it takes a time to cool it down after the pattern of a mold is transferred, and the productivity (throughput) for manufacturing imprint products becomes low.
- thermoplastic resin which can be used for manufacturing a sheet or a film like a substrate used for thermal imprint, is superior in thermal imprint characteristics (transferability, mold release characteristic, and the like), and improves a productivity (throughput), and a thermal imprint method using the same.
- the present invention enables the development of an ideal polymer for nanoimprinting co-relating the glass transition temperature and MFR of the polymer.
- a cyclic-olefin-based thermoplastic resin of the invention is used for producing a sheet or a film, contains at least one of skeletons represented by the following chemical equation 1 or the following chemical equation 2 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy the following equation 1, and [M] ⁇ 30.
- R 1 to R 29 in the chemical equations 1, 2 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0.
- [M] in equation 1 represents a value of MFR at 260° C.
- Another resin for thermal imprint of the invention is used for producing a sheet or a film, comprises a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by the following chemical equation 3 or the following chemical equation 4 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M] ⁇ 20 and Tg>90° C.
- R 1 to R 29 in the chemical equations 3, 4 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0.
- [M] in equation 1 represents a value of MFR at 260° C.
- the cyclic-olefin-based thermoplastic resin should comprise a copolymer of cyclic-olefin represented by the following chemical equation 5 and x-olefin, or a polymer produced by hydrogenation after ring-opening polymerization of the cyclic-olefin.
- R 30 to R 48 in chemical equation 5 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0
- the resin for thermal imprint may contain greater than or equal to one additive.
- the additive should contain at least either one of an anti-oxidizing agent or a lubricant.
- a resin containing a skeleton represented by the chemical equation 3 is a copolymer of cyclic-olefin represented by the following chemical equation 6 and ethylene.
- R 30 to R 48 in the chemical equation 6 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0)
- a thermal imprint method of the invention comprises: pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the foregoing resin for thermal imprint, thereby transferring a pattern of the mold.
- Tg glass transition temperature
- Another thermal imprint method of the invention comprises steps of: pressing a mold against an injection molded body comprising the foregoing resin for thermal imprint; and releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint ⁇ 25° C.
- Tg glass transition temperature
- thermal imprint method of the invention comprises: pressing a mold against a sheet or a film comprising the foregoing resin for thermal imprint at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
- the invention relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 7 or the following chemical equation 8 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M] ⁇ 30.
- R 1 to R 29 in the chemical equations 7, 8 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0.
- [M] in equation 1 represents a value of MFR at 260° C.
- the invention also relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 9 or the following chemical equation 10 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M] ⁇ 20 and Tg>90° C.
- R 1 to R 29 in the chemical equations 9, 10 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to 0.
- [M] in equation 1 represents a value of MFR at 260° C.
- a cyclic-olefin-based thermoplastic resin which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., enables a thermal imprint at a low temperature and a low pressure, thereby improving the imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput).
- a cyclic-olefin-based thermoplastic resin to which the invention is applied is a copolymer of cyclic-olefin and a-olefin, i.e., a copolymer with a-olefin containing a repeating unit indicated by a following chemical equation 11 and derived from cyclic-olefin, or a polymer that hydrogen is added to cyclic-olefin indicated by a chemical equation 12 undergone ring-opening polymerization.
- R 1 to R 29 in the chemical equation 11 and the chemical equation 12 may differ, or may be same, and each of which is a substituent containing hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen, or sulfur, and forms a monocyclic or polycyclic structure with one another.
- m and n are integers greater than or equal to zero.
- Cyclic-olefin monomer which constitutes the foregoing resin has a structure indicated by a chemical equation 13, and examples of preferable monomer are, for example, bicyclo[2,2,1]hept-2-ene(norbornene), 5-methylbicyclo[2,2, 1]hept-2-ene, 7-methybicyclo[2,2,1]hept-2-ene, 5-ethylbicyclo[2,2,1]hept-2-ene, 5-propylbicyclo[2,2,1]hept-2-ene, 5-n-butylbicyclo[2,2,1]hept-2-ene, 5-isobutylbicyclo[2,2,1]hept-2-ene 1,4-dimnethylbicyclo[2,2,1]hept-2-ene, 5-bromobicyclo[2,2,1]hept-2-ene, 5-chlorobicyclo[2,2,1]hept-2-ene, 5-fluorobicyclo[2,2,1]hept-2-
- R 30 to R 48 in the chemical equation 13 may differ or may be same, and each of which is a substituent including hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen and sulfur, and forms a monocyclic or polycyclic structure with each other.
- m and n are integers greater than or equal to zero.
- ⁇ -olefin suitably used for the copolymer indicated by the chemical equation 11 is ⁇ -olefin having a carbon number of 2 to 20, preferably, a carbon number of 2 to 10, and includes, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and those can be used individually or combined. Ethylene and propylene are preferable in those, and ethylene is particularly preferable from the standpoint of practical aspects, such as copolymer characteristic, and economic efficiency.
- the preferable mole ratio ( ⁇ -olefin/cyclic-olefn) between the ⁇ -olefin and the cyclic-olefin is within a range from 10/90 to 90/10, and further preferably, with in a range from 30/70 to 70/30.
- the mole ratio in copolymer is decided based on 13 C-NMR (400 MHz, temperature: 120° C./solvent: 1,2,4-trichlorobenzene/1,1,2,2-deuterated tetrachloroethane mixing system).
- the thermal imprint resin of the invention is adjusted in such a way that the glass transition temperature Tg (° C.) thereof and a value ([M]) of MFR at 260° C. satisfy the following equation 1.
- the weight average molecular weight Mw of the cyclic-olefin-based thermoplastic resin indicated by the chemical equation 11 or the chemical equation 12 is within 10,000 to 1,000,000, preferably, 20,000 to 500,000, and further preferably, 50,000 to 300,000, and the value [M] of MFR at 260° C. is less than or equal to 30, preferably, less than or equal to 20, and further preferably, less than or equal to 10. Accordingly, the strength of the resin becomes high, so that the imprint characteristics (transferability, mold release characteristic, and the like) can be improved without deteriorating the fluidity of the resin.
- the heat resistance of the resin should be high, and the glass transition temperature should be greater than or equal to 80° C., preferably, greater than or equal to 90° C., and further preferably, higher than the boiling temperature of water, i.e., beyond 100° C. in view of the practicality.
- a polymerization method for producing the resin is not limited to any particular ones, and well-known methods, such as a method of coordination polymerization using Ziegler-Natta catalyst or single-site catalyst, and further, causing a copolymer to be subjected to hydrogen addition in accordance with necessity, and a method of adding hydrogen after ring-opening polymerization using metathesis polymerization catalyst.
- a method of adding hydrogen well-known methods can be employed, and this can be carried out using a catalyst containing metal components, such as nickel, and palladium.
- Examples of the single-site catalyst used for producing the copolymer indicated by, for example, the chemical equation 11 are various kinds of metallocene compounds, and methylene(cyclopentadienyl)(tetracyclopentadienyl)zirconiumdichloride or the like disclosed in, for example, Japanese Unexamined Patent Application Laid-open Publication No. 2003-82017 can be preferably used.
- a promoter used for a polymerization reaction is not limited to any particular one, but methyl aluminoxanes can be used preferably, and other organic aluminum compounds may coexist and polymerize in accordance with a reaction. Such a polymerization reaction can be preferably carried out within a range from a room temperature (25° C.
- An organic solvent used for a polymerization reaction is not limited to any particular one, and for example, aromatic solvents, such as benzene, toluene, xylene, and ethyl benzene, saturated hydrocarbon solvents, such as hexane, cyclohexane, heptane, methyl cyclohexane, and octane, or a mixed solvent thereof can be preferably used.
- aromatic solvents such as benzene, toluene, xylene, and ethyl benzene
- saturated hydrocarbon solvents such as hexane, cyclohexane, heptane, methyl cyclohexane, and octane, or a mixed solvent thereof can be preferably used.
- hetero atoms such as oxygen atoms and sulfur atoms can be arbitrarily introduced by a radical reaction.
- additives such as an anti-oxidizing agent, a heat resistance stabilizer, a weathering stabilizer, a light stabilizer, an antistatic agent, a slipping agent, anti-blocking agent, an anti-fog additive, a lubricant, a color, a pigment, a natural oil, a synthetic oil, and a wax
- additives such as an anti-oxidizing agent, a heat resistance stabilizer, a weathering stabilizer, a light stabilizer, an antistatic agent, a slipping agent, anti-blocking agent, an anti-fog additive, a lubricant, a color, a pigment, a natural oil, a synthetic oil, and a wax
- additives such as an anti-oxidizing agent, a heat resistance stabilizer, a weathering stabilizer, a light stabilizer, an antistatic agent, a slipping agent, anti-blocking agent, an anti-fog additive, a lubricant, a color, a pigment, a natural oil, a synthetic oil
- additives like fluorine containing non-ionic surfactant or silocone containing leveling material could be used to reduce surface roughness of a sheet or a film.
- addition of an oxidizing agent prevents an oxidization of the resin when heated, a creation of a gel originating from the staining of the resin and a bridge formation of the resin molecular chain, and a deterioration of physical property due to a disconnection of the resin molecular chain.
- addition of a lubricant improves the mold release characteristic, after imprint, and the productivity (throughput) of imprint products. Furthermore, there is an effectiveness such that the resin can be easily put into a pattern on a mold when fabricating the resin.
- a rubber component can be added to improve the durability of the resin plate, and a well-known compound can be used.
- Examples of the applications of the imprint product are optical devices, such as an optical waveguide, a light guiding plate, and a diffraction grating, biochips, fluidic devices, such as a micro flow channel, and a micro reactor, media for saving data, and circuit substrates.
- optical devices such as an optical waveguide, a light guiding plate, and a diffraction grating
- biochips such as a micro flow channel, and a micro reactor, media for saving data, and circuit substrates.
- the method of manufacturing a sheet or a film is not limited to any particular one, and a well-known method of the extrusion molding, dipping method, solution casting, spin coating method, or the like can be applied.
- the thickness can be arbitrarily selected in accordance with an application of an imprint product, and molding is possible if the thickness is less than or equal to 500 ⁇ m.
- the sheet or the film using the thermal imprint resin of the invention can be formed in any shapes, it is preferable that the thickness is less than or equal to 300 ⁇ m, and more preferably less than or equal to 150 ⁇ m.
- Various products can be used as a device for imprinting, and can be selected arbitrarily.
- Various sizes such as less than or equal to 100 ⁇ m, less than or equal to 50 ⁇ m, less than or equal to 10 ⁇ m, less than or equal to 1 ⁇ m, and less than or equal to 500 nm can be selected as the size of a transferred pattern for the thermal imprint resin of the invention.
- the molding pressure in performing imprinting should be less than or equal to 3.0 MPa, and more preferably, less than or equal to 2.5 MPa.
- the retention time in performing molding should be less than or equal to 1000 seconds, more preferably, less than or equal to 600 seconds.
- the polymer film or sheet could be supported by a substrate of a polymer like poly carbonates, poly acryls, poly imides or graphite or metal like aluminum, stainless steel, etc, during the imprinting process.
- a polymer substrate is used as a support, the glass transition temperature of the said polymer should be higher than the temperature at which the imprinting is performed.
- the film on substrate could be used directly.
- the temperature of the mold it is preferable to reduce the temperature of the mold, and to shorten the retention time in performing molding. This is because that if the mold temperature is low, the cooling time can be shortened, and if the retention time at which the mold and the sheet or the film are pressed is short, then the molding time can be shortened.
- a sheet or a film comprised of the resin of the invention it is preferable to use a sheet or a film comprised of the resin of the invention, and to set the temperature in performing molding to less than or equal to the glass transition temperature Tg+80° C., and more preferably, less than or equal to Tg+65° C. It is preferable that the temperatures of the mold in mold releasing and the sheet or the film should be greater than or equal to Tg ⁇ 40° C., and more preferably, greater than or equal to Tg ⁇ 25° C.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mw/Mn molecular weight fractionation
- Film or sheet could be fabricated either by the usage of Labo Plastomill D-2025 from Toyoseiki or by spin coating in a SC-300 spin coater from E.H.C Corporation or by casting using an applicator on a glass plate followed by baking, drying and annealing.
- Samples 1 to 8 were sheets or films made of resins which satisfied the foregoing equation 1
- samples 9 and 10 were sheets or films made of resins which did not satisfy the equation 1.
- polymers used for sheets or films contained an anti-oxidizing agent and a lubricant, as long as any particular explanations will be given for product examples.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 111° C.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+30° C. i.e., 164
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+30° C. i.e., 164°
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+30° C. i.e., 164° C.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+35° C. i.e., 169° C.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+35° C. i.e., 169° C.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 111° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+30° C. i.e., 164° C
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 111° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 169° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 111° C.
- Tg+35° C. i.e., 169° C
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ml/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C.(112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C
- Sample 3 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 86° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 144° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (86° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 86° C.
- Sample 3 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 86° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 144° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (86° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 86° C.
- Sample 3 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 104° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 174° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (104° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 104° C.
- Tg ⁇ 5° C. i.e., 104° C.
- Sample 3 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 104° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 174° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (104° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 104° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ ml/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+15° C. (i.e., 153° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+15° C. (i.e., 153° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+55° C. (i.e., 193° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+55° C. i.e., 193°
- Tg ⁇ 23° C. i.e., 115° C.
- Tg+30° C. i.e., 168° C
- Tg ⁇ 23° C. i.e., 115° C.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+55° C. i.e., 193° C.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Tg+30° C. i.e., 168° C
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 115° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 750 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 115° C.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+65° C. i.e., 203° C.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+55° C. (i.e., 193° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 133° C.
- Tg+55° C. i.e., 193° C.
- Sample 5 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 131° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 201° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (131° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 131° C.
- Tg+65° C. i.e., 201° C
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 82° C.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 82° C.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+15° C. (i.e., 120° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 82° C.
- Sample 6 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 100° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+55° C. (i.e., 160° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (100° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 100° C.
- Tg+55° C. i.e. 160° C.
- Tg ⁇ 23° C. i.e., 82° C.
- Tg ⁇ 5° C. i.e., 100° C.
- Tg+55° C. i.e. 160° C.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 82° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 23° C. i.e., 82° C.
- Sample 6 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 100° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+55° C. (i.e., 160° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (100° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 5° C. i.e., 100° C.
- Tg+55° C. i.e. 160° C.
- Sample 7 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 15° C. (i.e., 120° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 15° C. (120° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Tg ⁇ 15° C. i.e. 120° C.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+30° C. i.e., 165°
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+30° C. i.e., 165°
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+30° C. i.e., 165° C
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170°
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170° C
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+35° C. i.e., 170°
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+15° C. (i.e., 150° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+15° C. i.e. 150° C.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+15° C. (i.e., 150° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+15° C. i.e. 150° C.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg ⁇ 23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg ⁇ 23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Tg ⁇ 23° C. i.e., 112° C.
- Tg+30° C. i.e., 165° C.
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 5° C. i.e., 127° C.
- Tg+65° C. i.e.,
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 127° C), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 5° C. i.e., 127° C
- Tg+65° C. i.e., 197
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 5° C. i.e., 127° C.
- Tg+65° C. i.e.,
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg ⁇ 5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 ⁇ m/depth 1 ⁇ m) which was preheated to a molding set temperature Tg+55° C. (i.e., 187° C.) was pressed against the surface of the film at a speed of 100 ⁇ m/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg ⁇ 5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 ⁇ m/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Tg ⁇ 5° C. i.e., 127° C.
- Tg+55° C. i.e.,
- the film manufactured from a cyclic-olefin-based thermoplastic resin having a specific correlation (indicated by equation 1) between a glass transition temperature Tg (° C.) and MFR at 260° C. has a superior thermal imprint characteristic at a low temperature and a low pressure, and can provide a good transferred pattern. Furthermore, it becomes apparent that the film manufactured from a cyclic-olefin-based thermoplastic resin which does not have a specific correlation (indicated by equation 1) between a glass transition temperature Tg (° C.) and MFR at 260° C. can't provide a good transferred pattern only because the film formed a stretching or distortion of pattern.
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Abstract
A cyclic-olefin-based thermoplastic resin for thermal imprint to be used in the production of a sheet or a film which contains at least one of skeletons represented by the following chemical equation 1 or the following chemical equation 2 in a main chain. The glass transition temperature Tg (° C.) and the value ([M]) of MFR at 260° C. satisfy the following equation 1, and [M]<30. The thermal imprint characteristics (transferability, mold release characteristic, and the like) are superior and the productivity (throughput) is improved.
Description
- The present invention relates to a resin for thermal imprint. More specifically, the present invention relates to a cyclic-olefin-based thermoplastic resin which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., and can be used for producing a sheet or a film.
- As the optical fields for optical communications, optical disks, displays, optical sensors, and the like dramatically develop, achieving both performance and cost becomes important for optical resin materials. Expectations for transparent resin materials which are easy to process become large in fields of biochips, micro reactors, and the like, in lieu of glasses. In all fields, processing of a base material surface, in particular, microprocessing becomes requisite, and the microprocessing becomes an important technology in a recent semiconductor field where integration becomes remarkable. Conventionally, to form a minute pattern on the surface of a transparent material, schemes of cutting the surface mechanically or of printing a pattern using a resist, a thermo, ultraviolet, or electron radiation curing resin, or the like are used. In particular, to cope up with the present trend and future need for miniaturization of various devices, several different patterning methods are under continuing development. Injection molding has its limitation below 500 μm of film thickness. However, various advanced devices including anti reflecting film or coating requires patterning on a sheet or a film with thickness much below the limit of injection molding.
- According to the mechanical cutting, however, there is a problem such that an advanced and complex processing technique is required. According to the pattern printing using a resist or the like, steps thereof are complicated, and there is a problem in the durability, such as peeling of a printed pattern. Further, as patterns become minuter, a mechanism which controls a whole process highly precisely becomes requisite, so that the cost issue becomes not negligible.
- To cope with such problems, there is proposed a thermal imprint method for forming a minute pattern at low cost. That is, this is a method of pressing a mold, having a minute pattern heated more than or equal to a glass transition temperature of a resin, against a resin substrate, and of transferring the minute pattern of the mold on the melted resin surface.
- Disclosed so far to improve the thermal imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput) are a scheme of providing an insulator to shorten a cycle of temperature rising and cooling (see, for example, patent literature 1), and a scheme of providing an ultrasonic generation mechanism to reduce the melt viscosity by ultrasonic (see, for example, patent literature 2). However, there are few literatures which mentioned materials used for thermal imprint, and development of the materials for thermal imprint is desired.
- In general, examples of materials used for thermal imprint are resin materials, glasses, metals, and the like. The resin materials can be molded at a lower temperature in comparison with imprinting to metals or glasses, thus advantageous for the manufacturing cost.
- An example of resins is a (meta) acrylic resin represented by polymethacrylic acid (PMMA) or a polycarbonate resin, but have a problem such that the heat resistance is low and size distortion occurs due to water absorption. Further, controlling a balance between the fluidity and the solidification is difficult, so that it is difficult to maintain and use a minutely-transferred pattern (see, for example, patent literature 3).
- On the other hand, as a resin having both heat resistance and dimension stability originating from the low water absorption coefficient, there are cyclic-olefin-based thermoplastic resins. In general, the cyclic-olefin-based thermoplastic resins are superior in the transparency, the chemical resistance property, and the low moisture absorption characteristic, and its heat resistance can be easily controlled by the structure of the cyclic-olefin or the contained amount of the cyclic-olefin in the resin. The resin has a low viscosity, and a short relaxation time (time necessary for filling the resin in the pattern of a mold), and is less adhered to the mold, and is superior in the transfer accuracy of a minute pattern, so that application as a thermal imprint material is expected as having a good productivity (see, for example, non-patent literature 1).
- Patent Literature 1: Japanese Unexamined Patent Application Laid-open Publication No.2002-361500
- Patent Literature 2: Japanese Unexamined Patent Application Laid-open Publication No.2004-288811
- Patent Literature 3: Japanese Unexamined Patent Application Laid-open Publication No. 2000-158532
- Non-patent Literature 1: J. Mater. Chem., 2000, volume 10, page 2634
- Non-patent Literature 2: Nanoimprint Lithography in Topas, a highly UV-transparent and chemically resistant thrmoplast, T. Nielsen, D. Nilsson, et al.
- However, conventional cyclic-olefin-based thermoplastic resins are not ones that the resin properties, such as a glass transition temperature Tg (° C.) and the fluidity are developed for the process of thermal nano-imprint, but require a high molding temperature and a large molding pressure, thus having insufficient thermal imprint characteristics (transferability, mold release characteristic, and the like). Moreover, a long molding time is required, so that the productivity (throughput) is low. For example, one disclosed in the foregoing non-patent literature 1 has a high molding temperature of 240° C., so that it takes a time to cool it down after the pattern of a mold is transferred, and the productivity (throughput) for manufacturing imprint products becomes low. In a non patent literature, as cited in 2, a polymer with a low Glass Transition temperature of 80° C. have been used however, the imprinting is performed at 90° C. above the glass transition temperature of the polymer for 5 min with a pressure of 2000N, making it a process with prolonged cooling time having a low practical or commercial impact, similar to that in citation 1. It is our experience that an optimized polymer for injection molding does not yield well in thermal nanoimprinting or, in other words, an ideal polymer film for thermal nanoimprinting would have to have a different characteristics that that of an ideal polymer for injection molding.
- This is primarily because that a correlation between the resin properties, in particular, a glass transition temperature and MFR which becomes the barometer of the fluidity of the resin, and a correlation between an imprint conditions (molding temperature, molding pressure, mold release temperature, and the like) to the resin and the imprint characteristics (transferability, mold release characteristic, and the like) are not figured out.
- Therefore, it is an object of the invention to provide a cyclic-olefin-based thermoplastic resin which can be used for manufacturing a sheet or a film like a substrate used for thermal imprint, is superior in thermal imprint characteristics (transferability, mold release characteristic, and the like), and improves a productivity (throughput), and a thermal imprint method using the same.
- To overcome the above mentioned problem, the present invention enables the development of an ideal polymer for nanoimprinting co-relating the glass transition temperature and MFR of the polymer.
- That is, a cyclic-olefin-based thermoplastic resin of the invention is used for producing a sheet or a film, contains at least one of skeletons represented by the following chemical equation 1 or the following chemical equation 2 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy the following equation 1, and [M]<30.
- (R1 to R29 in the chemical equations 1, 2 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)
- Another resin for thermal imprint of the invention is used for producing a sheet or a film, comprises a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by the following chemical equation 3 or the following chemical equation 4 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M] <20 and Tg>90° C.
- (R1 to R29 in the chemical equations 3, 4 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)
- In this case, it is preferable that the cyclic-olefin-based thermoplastic resin should comprise a copolymer of cyclic-olefin represented by the following chemical equation 5 and x-olefin, or a polymer produced by hydrogenation after ring-opening polymerization of the cyclic-olefin.
- (R30 to R48 in chemical equation 5 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0)
- The resin for thermal imprint may contain greater than or equal to one additive. In this case, it is preferable that the additive should contain at least either one of an anti-oxidizing agent or a lubricant.
- Further, it is preferable that a resin containing a skeleton represented by the chemical equation 3 is a copolymer of cyclic-olefin represented by the following chemical equation 6 and ethylene.
- (R30 to R48 in the chemical equation 6 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0)
- A thermal imprint method of the invention comprises: pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the foregoing resin for thermal imprint, thereby transferring a pattern of the mold.
- Another thermal imprint method of the invention comprises steps of: pressing a mold against an injection molded body comprising the foregoing resin for thermal imprint; and releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.
- Other thermal imprint method of the invention comprises: pressing a mold against a sheet or a film comprising the foregoing resin for thermal imprint at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
- The invention relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 7 or the following chemical equation 8 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M]<30.
- (R1 to R29 in the chemical equations 7, 8 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)
- The invention also relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 9 or the following chemical equation 10 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M]<20 and Tg>90° C.
- (R1 to R29 in the chemical equations 9, 10 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)
- Using a cyclic-olefin-based thermoplastic resin, which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., enables a thermal imprint at a low temperature and a low pressure, thereby improving the imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput).
- Further, by applying imprint conditions (molding temperature, molding pressure, mold release temperature, and the like) to a cyclic-olefin-based thermoplastic resin having a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., the thermal imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput) can be further improved.
- An embodiment of the invention will be explained in detail with reference to the drawings.
- A cyclic-olefin-based thermoplastic resin to which the invention is applied is a copolymer of cyclic-olefin and a-olefin, i.e., a copolymer with a-olefin containing a repeating unit indicated by a following chemical equation 11 and derived from cyclic-olefin, or a polymer that hydrogen is added to cyclic-olefin indicated by a chemical equation 12 undergone ring-opening polymerization.
- R1 to R29 in the chemical equation 11 and the chemical equation 12 may differ, or may be same, and each of which is a substituent containing hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen, or sulfur, and forms a monocyclic or polycyclic structure with one another. Note that m and n are integers greater than or equal to zero.
- Cyclic-olefin monomer which constitutes the foregoing resin has a structure indicated by a chemical equation 13, and examples of preferable monomer are, for example, bicyclo[2,2,1]hept-2-ene(norbornene), 5-methylbicyclo[2,2, 1]hept-2-ene, 7-methybicyclo[2,2,1]hept-2-ene, 5-ethylbicyclo[2,2,1]hept-2-ene, 5-propylbicyclo[2,2,1]hept-2-ene, 5-n-butylbicyclo[2,2,1]hept-2-ene, 5-isobutylbicyclo[2,2,1]hept-2-ene 1,4-dimnethylbicyclo[2,2,1]hept-2-ene, 5-bromobicyclo[2,2,1]hept-2-ene, 5-chlorobicyclo[2,2,1]hept-2-ene, 5-fluorobicyclo[2,2,1]hept-2-ene, 5,6-dimethylbicyclo[2,2,1]hept-2-ene, dicyclopentadiene, tricyclopentadiene, tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 5,10-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 2,10-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 11,12-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 2,7,9-trimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 9-ethyl-2,7-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 9-isobutyl-2,7-dimetyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 9,11,12-triethyltetmcyclo[4,4,0,12.5,17.10]-3-dodecene, 9-ethyl-11,12-dimethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 9-isobutyl-11,12-dimethyltetmcyclo[4,4,0,12.5, 17.10]-3-dodecene, 5,8,9,10-tetramethyltetracyclo[4,4,0,12.5, 17.10]-3-dodecene, 8-hexyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-stearyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-methyl-9-ethyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-cyclohexyltetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-ethylidenetetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-chlorotetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-bromotetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-fluorotetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8,9-dichlorotetmcyclo[4,4,0,12.5,17.10]-3-dodecene, hexacyclo[6,6,1,13.6,110.13,02.7, 09.14]-4-deptadecene, 12-methylhexacyclo[6,6,1,13.6,110.13,02.7, 09.14])-4-deptadecene, 12-ethylhexacyclo[6,6,1,13.6,110.13,02.7, 09.14]-4-deptadecene, 12-isobutylhexacyclo[6,6,1,13.6, 110.13,02.7,09.14]-4-deptadecene, 1,6,10-trimethyl-12-isobutylhexacyclo[6,6,1,13.6,110.13,02.7,09.4]-4-deptadecene, 5-methyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-ethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-n-propyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-n-butyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5,6-dimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-methyl-6-ethyl-5-phenylbicyclo[2,2,1]hept-2-ene, 5,6,6-trimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 1,4,5-trimethylbicyclo[2,2,1]hept-2-ene, 5,6-diethyl-5-phenylbicyclo[2,2,1]hept-2-ene, 5-bromo-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-chloro-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-fluoro-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(tert-butylphenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(bromophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(chlorophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(fluorophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(a-naphthyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-antracenyl-bicyclo[2,2,1]hept-2-ene, 8-methyl-8-phenyl-tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-ethyl-8-phenyl-tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-n-propyl-8-phenyl-tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-n-butyl-8-phenyl-tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 8-chloro-8-phenyl-tetracyclo[4,4,0,12.5,17.10]-3-dodecene, 11-methyl-11-phenyl-hexacyclo[6,6,1, 13.6,110.13,0 2.7,09.14]-4-heptadecene, 1,4-methano-4a,9,9-trimethyl-1,4,9a-trihydrofluorene. Such various monomers can be basically made by a thermal Diels-Alder reaction of corresponding dienes and olefins, and adding hydrogen or the like appropriately makes it possible to produce a desired monomer.
- R30 to R48 in the chemical equation 13 may differ or may be same, and each of which is a substituent including hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen and sulfur, and forms a monocyclic or polycyclic structure with each other. Note that m and n are integers greater than or equal to zero.
- An example of α-olefin suitably used for the copolymer indicated by the chemical equation 11 is α-olefin having a carbon number of 2 to 20, preferably, a carbon number of 2 to 10, and includes, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and those can be used individually or combined. Ethylene and propylene are preferable in those, and ethylene is particularly preferable from the standpoint of practical aspects, such as copolymer characteristic, and economic efficiency.
- In the copolymer indicated by the chemical equation 11, the preferable mole ratio (α-olefin/cyclic-olefn) between the α-olefin and the cyclic-olefin is within a range from 10/90 to 90/10, and further preferably, with in a range from 30/70 to 70/30. The mole ratio in copolymer is decided based on 13C-NMR (400 MHz, temperature: 120° C./solvent: 1,2,4-trichlorobenzene/1,1,2,2-deuterated tetrachloroethane mixing system).
- The thermal imprint resin of the invention is adjusted in such a way that the glass transition temperature Tg (° C.) thereof and a value ([M]) of MFR at 260° C. satisfy the following equation 1.
-
Tg(° C.)>219×log[M]−160 [Equation 1] - The weight average molecular weight Mw of the cyclic-olefin-based thermoplastic resin indicated by the chemical equation 11 or the chemical equation 12 is within 10,000 to 1,000,000, preferably, 20,000 to 500,000, and further preferably, 50,000 to 300,000, and the value [M] of MFR at 260° C. is less than or equal to 30, preferably, less than or equal to 20, and further preferably, less than or equal to 10. Accordingly, the strength of the resin becomes high, so that the imprint characteristics (transferability, mold release characteristic, and the like) can be improved without deteriorating the fluidity of the resin.
- In considering the application of the resin on which a minute pattern is transferred by thermal imprint, it is preferable that the heat resistance of the resin should be high, and the glass transition temperature should be greater than or equal to 80° C., preferably, greater than or equal to 90° C., and further preferably, higher than the boiling temperature of water, i.e., beyond 100° C. in view of the practicality.
- A polymerization method for producing the resin is not limited to any particular ones, and well-known methods, such as a method of coordination polymerization using Ziegler-Natta catalyst or single-site catalyst, and further, causing a copolymer to be subjected to hydrogen addition in accordance with necessity, and a method of adding hydrogen after ring-opening polymerization using metathesis polymerization catalyst. As a method of adding hydrogen, well-known methods can be employed, and this can be carried out using a catalyst containing metal components, such as nickel, and palladium. Examples of the single-site catalyst used for producing the copolymer indicated by, for example, the chemical equation 11 are various kinds of metallocene compounds, and methylene(cyclopentadienyl)(tetracyclopentadienyl)zirconiumdichloride or the like disclosed in, for example, Japanese Unexamined Patent Application Laid-open Publication No. 2003-82017 can be preferably used. A promoter used for a polymerization reaction is not limited to any particular one, but methyl aluminoxanes can be used preferably, and other organic aluminum compounds may coexist and polymerize in accordance with a reaction. Such a polymerization reaction can be preferably carried out within a range from a room temperature (25° C. or so) to 200° C., but it is desirable to carry out such a reaction within a range from 40 to 150° C. in view of the reactivity and the stability of a catalyst. An organic solvent used for a polymerization reaction is not limited to any particular one, and for example, aromatic solvents, such as benzene, toluene, xylene, and ethyl benzene, saturated hydrocarbon solvents, such as hexane, cyclohexane, heptane, methyl cyclohexane, and octane, or a mixed solvent thereof can be preferably used. After the resin is produced, hetero atoms, such as oxygen atoms and sulfur atoms can be arbitrarily introduced by a radical reaction.
- In accordance with necessity, greater than or equal to one of additives, such as an anti-oxidizing agent, a heat resistance stabilizer, a weathering stabilizer, a light stabilizer, an antistatic agent, a slipping agent, anti-blocking agent, an anti-fog additive, a lubricant, a color, a pigment, a natural oil, a synthetic oil, and a wax, can be added and mixed, and the mix ratio thereof can be set arbitrarily. Additives (anti-oxidizing agent, lubricant, and the like) are not limited to any particular ones, and well-known compounds can be used preferably.
- Additionally, additives like fluorine containing non-ionic surfactant or silocone containing leveling material could be used to reduce surface roughness of a sheet or a film.
- According to the invention, addition of an oxidizing agent prevents an oxidization of the resin when heated, a creation of a gel originating from the staining of the resin and a bridge formation of the resin molecular chain, and a deterioration of physical property due to a disconnection of the resin molecular chain.
- According to the invention, addition of a lubricant improves the mold release characteristic, after imprint, and the productivity (throughput) of imprint products. Furthermore, there is an effectiveness such that the resin can be easily put into a pattern on a mold when fabricating the resin.
- Further, without deteriorating the physical properties required in the application fields of an imprint product, a rubber component can be added to improve the durability of the resin plate, and a well-known compound can be used.
- Examples of the applications of the imprint product are optical devices, such as an optical waveguide, a light guiding plate, and a diffraction grating, biochips, fluidic devices, such as a micro flow channel, and a micro reactor, media for saving data, and circuit substrates.
- The method of manufacturing a sheet or a film is not limited to any particular one, and a well-known method of the extrusion molding, dipping method, solution casting, spin coating method, or the like can be applied. The thickness can be arbitrarily selected in accordance with an application of an imprint product, and molding is possible if the thickness is less than or equal to 500 μm. The sheet or the film using the thermal imprint resin of the invention can be formed in any shapes, it is preferable that the thickness is less than or equal to 300 μm, and more preferably less than or equal to 150 μm.
- Various products can be used as a device for imprinting, and can be selected arbitrarily. Various sizes, such as less than or equal to 100 μm, less than or equal to 50 μm, less than or equal to 10 μm, less than or equal to 1 μm, and less than or equal to 500 nm can be selected as the size of a transferred pattern for the thermal imprint resin of the invention.
- Next, an explanation will be given of a method of performing imprinting on a sheet or a film comprising the resin of the invention.
- To realize a process having the improved imprint characteristics (transferability, mold release characteristic, and the like), it is preferable to reduce a molding pressure and to shorten the retention time at molding. This is because that if the molding pressure when performing imprinting is too high and the retention time of a pressure is too long, the resin adheres to the mold, so that the pattern is elongated or damaged in mold releasing, and the transfer precision of the pattern is reduced. Specifically, in using a sheet or a film of the resin of the invention, the molding pressure in performing imprinting should be less than or equal to 3.0 MPa, and more preferably, less than or equal to 2.5 MPa. Further, the retention time in performing molding should be less than or equal to 1000 seconds, more preferably, less than or equal to 600 seconds.
- The polymer film or sheet could be supported by a substrate of a polymer like poly carbonates, poly acryls, poly imides or graphite or metal like aluminum, stainless steel, etc, during the imprinting process. In case a polymer substrate is used as a support, the glass transition temperature of the said polymer should be higher than the temperature at which the imprinting is performed. In case a film is cast on a substrate of aluminum or silicon, etc, the film on substrate could be used directly.
- Further, to realize a process having the improved productivity (throughput), it is preferable to reduce the temperature of the mold, and to shorten the retention time in performing molding. This is because that if the mold temperature is low, the cooling time can be shortened, and if the retention time at which the mold and the sheet or the film are pressed is short, then the molding time can be shortened.
- Specifically, it is preferable to use a sheet or a film comprised of the resin of the invention, and to set the temperature in performing molding to less than or equal to the glass transition temperature Tg+80° C., and more preferably, less than or equal to Tg+65° C. It is preferable that the temperatures of the mold in mold releasing and the sheet or the film should be greater than or equal to Tg−40° C., and more preferably, greater than or equal to Tg−25° C.
- Examples of the invention will be explained below, but the invention should not be limited to the following examples.
- Regarding the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight fractionation (Mw/Mn) of the resin to be used, an GPC device manufactured by Wasters was used by the gel permeation chromatography method (GPC), and those were measured under a condition such that column: K-805L/K-806L manufactured by Shodex, column temperature: 40° C., solvent: chloroform, flow rate: 0.8 ml/minute. The glass transition temperature Tg (° C.) of the resin used was acquired from the heat absorption peak in heat up using a differential scanning calorimeter (model: EXSTAR 6000, DSC 6200) manufactured by SEIKO. Further, regarding the value [M] of MFR at 260° C., the MELT INDEXER (model: L248-2531) manufactured by TECHNOL SEVEN Co., Ltd. was used, and a value measured at a loading of 2.16 kgf.
- Film or sheet could be fabricated either by the usage of Labo Plastomill D-2025 from Toyoseiki or by spin coating in a SC-300 spin coater from E.H.C Corporation or by casting using an applicator on a glass plate followed by baking, drying and annealing.
- For imprint evaluations, an imprint device (VX-2000N-US) manufactured by SCIVAX was used, and the evaluations were carried out under condition described in the examples, respectively, using a mold of 30 mm by 30 mm. Table 1 shows imprint characteristics inherent to presence/absence of correlations (represented by equation 1) between a structure of a resin or a glass transition temperature Tg (° C.) and MFR at 260° C. For evaluation of imprint characteristics, acquired minute bumpy patterns were observed through an electronic microscope, and if a pattern similar to a mold was well transferred, a circular mark is filled, if a resin adhered to a mold, and a deficit of a pattern was formed, then a triangle mark is filled, and if a pattern failure (insufficient filling, elongation, deficit) was confirmed, then a cross mark is filled. if a resin adhered to a mold and there is a deficit or film peeling or overstretch, then a cross mark is filled.
- First, an explanation will be given of the production method of a sheet or a film used in the examples and comparative examples. Samples 1 to 8 were sheets or films made of resins which satisfied the foregoing equation 1, and samples 9 and 10 were sheets or films made of resins which did not satisfy the equation 1. Note that polymers used for sheets or films contained an anti-oxidizing agent and a lubricant, as long as any particular explanations will be given for product examples.
- Ethylene/norbornene copolymer (Tg=134° C., MFR=11 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 1) having a thickness of 100 μm was produced.
- Ethylene/norbornene copolymer (Tg=135° C., MFR=10 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 2) having a thickness of 90 μm was produced.
- Ethylene/norbornene copolymer (Tg=109° C., MFR=16 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 3) having a thickness of 100 μm was produced.
- Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=138° C., MFR=8 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 4) having a thickness of 110 μm was produced.
- Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=136° C., MFR=7 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 5) having a thickness of 110 μm was produced.
- Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=105° C., MFR=9 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 6) having a thickness of 100 μm was produced.
- A solution containing 15wt % of ethylene/norbornane type copolymer (Tg=135° C., MFR=10@260° C.) in diethyl benzene solvent is spin coated on a silicon wafer (400 rpm×5 s 2000 rpm×20 s) followed by baking (100° C.×15 min, 150° C.×30 min) and annealing (110° C.×30 min) to produce 1.3 μm thick coating (sample 7)
- Ethylene/norbornene copolymer (Tg=135° C., MFR=59 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 8) having a thickness of 100 μm was produced.
- Ethylene/norbornene copolymer (Tg=132° C., MFR=51 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 9) having a thickness of 90 Jim was produced.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: line/space (L/S)=1 μm/1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 169° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 169° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 164° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 1 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 111° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 169° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (111° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 ml/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C.(112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 2 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 3 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 86° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 144° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (86° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 3 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 86° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 144° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (86° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 3 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 104° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 174° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (104° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 3 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 104° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 174° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (104° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 3 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 104° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 174° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (104° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μml/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+15° C. (i.e., 153° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+15° C. (i.e., 153° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 193° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (I 15° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 193° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 168° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 115° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 173° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 750 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (115° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 203° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 4 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 133° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 193° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (133° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 5 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 131° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 201° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (131° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 82° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+15° C. (i.e., 120° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg−23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 100° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 160° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (100° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 82° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−5° C. (i.e., 100° C.), a mold (pattern: US=1 μm/1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 160° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (100° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 82° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 140° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (82° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 6 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 100° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 160° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (100° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 7 was fixed on a plate which was heated to a glass transition temperature Tg−15° C. (i.e., 120° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−15° C. (120° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that a good pattern without the elongation and flaking off was transferred.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+35° C. (i.e., 170° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 500 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+15° C. (i.e., 150° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: pillar, diameter 0.75 μm/depth 1 μm) which was preheated to a molding set temperature Tg+15° C. (i.e., 150° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 600 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: L/S=1 μm/1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 8 was fixed on a plate which was heated to a glass transition temperature Tg−23° C. (i.e., 112° C.), a mold (pattern: hole, diameter 1 μm/depth 1 μm) which was preheated to a molding set temperature Tg+30° C. (i.e., 165° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 10 seconds by that load. Thereafter, it was cooled to Tg−23° C. (112° C.) while maintaining the displacement of the mold, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated, so that the pattern was no good.
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 2000 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 127° C), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+65° C. (i.e., 197° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1500 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- Sample 9 was fixed on a stainless plate which was heated to a glass transition temperature Tg−5° C. (i.e., 127° C.), a mold (pattern: pillar, diameter 0.5 μm/depth 1 μm) which was preheated to a molding set temperature Tg+55° C. (i.e., 187° C.) was pressed against the surface of the film at a speed of 100 μm/second, and when the load sensor attached to the upper part of the mold reached 1750 N, it was held for 300 seconds by that load. Thereafter, it was cooled to Tg−5° C. (127° C.) while maintaining the load, and after the completion of cooling, the mold was released from the film at a speed of 10 μm/second. It was observed through an electronic microscope that the resin was elongated and flaked off, so that the pattern was no good.
- The above-mentioned results are summarized in Table 1.
-
TABLE 1 MOLD HOLD SAMPLE 1 SAMPLE 2 SAMPLE 3 SAMPLE 4 PATTERN SIZE TEMPERATURE LOAD TIME (Tg = 134° C.) (Tg = 135° C.) (Tg = 109° C.) (Tg = 138° C.) PILLAR diameter 0.5 μm/ Tg + 15 2000 N 600 s — — — ◯ depth 1 μm (EXAMPLE 32) diameter 0.75 μm/ — — — ◯ depth 1 μm (EXAMPLE 33) diameter 1 μm/ — — — — depth 1 μm diameter 0.5 μm/ Tg + 30 10 s ◯ — — ◯ depth 1 μm (EXAMPLE 1) (EXAMPLE 24) diameter 0.75 μm/ ◯ — — ◯ depth 1 μm (EXAMPLE 2) (EXAMPLE 25) diameter 1 μm/ ◯ — — ◯ depth 1 μm (EXAMPLE 3) (EXAMPLE 26) diameter 0.5 μm/ Tg + 35 500 N — ◯ — ◯ depth 1 μm (EXAMPLE 12) (EXAMPLE 30) diameter 0.75 μm/ — ◯ — ◯ depth 1 μm (EXAMPLE 13) (EXAMPLE 31) diameter 1 μm/ — — ◯ — depth 1 μm (EXAMPLE 20) diameter 0.5 μm/ 2000 N — ◯ — ◯ depth 1 μm (EXAMPLE 9) (EXAMPLE 27) diameter 0.75 μm/ — ◯ — ◯ depth 1 μm (EXAMPLE 10) (EXAMPLE 28) diameter 1 μm/ — ◯ ◯ ◯ depth 1 μm (EXAMPLE 11) (EXAMPLE 19) (EXAMPLE 29) diameter 0.5 μm/ Tg + 55 1750 N 300 s — — — ◯ depth 1 μm (EXAMPLE 36) Tg + 65 1500 N — — — ◯ (EXAMPLE 35) 1750 N — — — — 2000 N — — — ◯ (EXAMPLE 34) diameter 1 μm/ 1500 N — — ◯ — depth 1 μm (EXAMPLE 21) L/S 1 μm/1 μm Tg + 30 2000 N 10 s ◯ — — ◯ (EXAMPLE 4) (EXAMPLE 37) Tg + 35 500 N ◯ ◯ — — (EXAMPLE 5) (EXAMPLE 15) 300 s ◯ ◯ — ◯ (EXAMPLE 6) (EXAMPLE 16) (EXAMPLE 38) 2000 N 10 s — ◯ — — (EXAMPLE 14) Tg + 55 1500 N 300 s — — — ◯ (EXAMPLE 41) 1750 N — — — — Tg + 65 1500 N — — ◯ — (EXAMPLE 22) 1750 N — — — ◯ (EXAMPLE 40) 2000 N — — — ◯ (EXAMPLE 39) HOLE diameter 1 μm/ Tg + 30 2000 N 10 s ◯ — — ◯ depth 1 μm (EXAMPLE 7) (EXAMPLE 42) Tg + 35 500 N ◯ ◯ — — (EXAMPLE 8) (EXAMPLE 18) 750 N — — ◯ (EXAMPLE 43) 2000 N — ◯ — — (EXAMPLE 17) Tg + 55 1750 N 300 s — — — ◯ (EXAMPLE 46) Tg + 65 1500 N — — ◯ ◯ (EXAMPLE 23) (EXAMPLE 45) 2000 N — — — ◯ (EXAMPLE 44) MOLD SAMPLE 5 SAMPLE 6 SAMPLE 7 PATTERN SIZE TEMPERATURE LOAD HOLD TIME (Tg = 136° C.) (Tg = 105° C.) (Tg = 135° C.) PILLAR diameter 0.5 μm/ Tg + 15 2000 N 600 s — — — depth 1 μm diameter 0.75 μm/ — — — depth 1 μm diameter 1 μm/ — ◯ — depth 1 μm (EXAMPLE 50) diameter 0.5 μm/ Tg + 30 10 s — — — depth 1 μm diameter 0.75 μm/ — — — depth 1 μm diameter 1 μm/ — — — depth 1 μm diameter 0.5 μm/ Tg + 35 500 N — — — depth 1 μm diameter 0.75 μm/ — — — depth 1 μm diameter 1 μm/ — ◯ — depth 1 μm (EXAMPLE 49) diameter 0.5 μm/ 2000 N — — — depth 1 μm diameter 0.75 μm/ — — — depth 1 μm diameter 1 μm/ — ◯ ◯ depth 1 μm (EXAMPLE 48) (EXAMPLE 56) diameter 0.5 μm/ Tg + 55 1750 N 300 s — ◯ — depth 1 μm (EXAMPLE 51) Tg + 65 1500 N — — — 1750 N — — — 2000 N ◯ — — (EXAMPLE 47) diameter 1 μm/ 1500 N — — — depth 1 μm L/S 1 μm/1 μm Tg + 30 2000 N 10 s — — — Tg + 35 500 N — — — 300 s — — — 2000 N 10 s — ◯ — (EXAMPLE 52) Tg + 55 1500 N 300 s — — — 1750 N — ◯ — (EXAMPLE 53) Tg + 65 1500 N — — — 1750 N — — — 2000 N — — — HOLE diameter 1 μm/ Tg + 30 2000 N 10 s — — — depth 1 μm Tg + 35 500 N — — — 750 N — — — 2000 N — ◯ — (EXAMPLE 54) Tg + 55 1750 N 300 s — ◯ — (EXAMPLE 55) Tg + 65 1500 N — — — 2000 N — — — MOLD HOLD SAMPLE 8 SAMPLE 9 PATTERN SIZE TEMPERATURE LOAD TIME (Tg = 135° C.) (Tg = 132° C.) PILLAR diameter 0.5 μm/ Tg + 15 2000 N 600 s X — depth 1 μm (COMPARATIVE EXAMPLE 9) diameter 0.75 μm/ X — depth 1 μm (COMPARATIVE EXAMPLE 10) diameter 1 μm/ — — depth 1 μm diameter 0.5 μm/ Tg + 30 10 s X — depth 1 μm (COMPARATIVE EXAMPLE 1) diameter 0.75 μm/ X — depth 1 μm (COMPARATIVE EXAMPLE 2) diameter 1 μm/ X — depth 1 μm (COMPARATIVE EXAMPLE 3) diameter 0.5 μm/ Tg + 35 500 N X — depth 1 μm (COMPARATIVE EXAMPLE 7) diameter 0.75 μm/ X — depth 1 μm (COMPARATIVE) EXAMPLE 8) diameter 1 μm/ — — depth 1 μm diameter 0.5 μm/ 2000 N X — depth 1 μm (COMPARATIVE EXAMPLE 4) diameter 0.75 μm/ X — depth 1 μm (COMPARATIVE EXAMPLE 5) diameter 1 μm/ X — depth 1 μm (COMPARATIVE EXAMPLE 6) diameter 0.5 μm/ Tg + 55 1750 N 300 s — X depth 1 μm (COMPARATIVE EXAMPLE 16) Tg + 65 1500 N — X (COMPARATIVE EXAMPLE 15) 1750 N — X (COMPARATIVE EXAMPLE 14) 2000 N — X (COMPARATIVE EXAMPLE 13) diameter 1 μm/ 1500 N — — depth 1 μm L/S 1 μm/1 μm Tg + 30 2000 N 10 s X — (COMPARATIVE EXAMPLE 11) Tg + 35 500 N — — 300 s — — 2000 N 10 s — — Tg + 55 1500 N 300 s — — 1750 N — — Tg + 65 1500 N — — 1750 N — — 2000 N — — HOLE diameter 1 μm/ Tg + 30 2000 N 10 s X — depth 1 μm (COMPARATIVE EXAMPLE 12) Tg + 35 500 N — — 750 N — — 2000 N — — Tg + 55 1750 N 300 s — — Tg + 65 1500 N — — 2000 N — — - It becomes apparent from table 1 that the film manufactured from a cyclic-olefin-based thermoplastic resin having a specific correlation (indicated by equation 1) between a glass transition temperature Tg (° C.) and MFR at 260° C. has a superior thermal imprint characteristic at a low temperature and a low pressure, and can provide a good transferred pattern. Furthermore, it becomes apparent that the film manufactured from a cyclic-olefin-based thermoplastic resin which does not have a specific correlation (indicated by equation 1) between a glass transition temperature Tg (° C.) and MFR at 260° C. can't provide a good transferred pattern only because the film formed a stretching or distortion of pattern.
Claims (20)
1. A resin for thermal imprint and for producing a sheet or a film, the resin comprising a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by a following chemical equation 1 or a following chemical equation 2 in a main chain, and wherein:
a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and
R1 to R29 in chemical equations 1, 2 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and, [M] in equation 1 represents a value of MFR at 260° C.
2. A resin for thermal imprint and for producing a sheet or a film, the resin comprising a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by a following chemical equation 3 or a following chemical equation 4 in a main chain, and wherein:
a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and
R1 to R29 in chemical equations 3, 4 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and [M] in equation 1 represents a value of MFR at 260° C.
3. The resin for thermal imprinting of claim 2 , wherein the cyclic-olefin-based thermoplastic resin comprises a copolymer of cyclic-olefin represented by a following chemical equation 5 and α-olefin, or a polymer produced by hydrogenation after ring-opening polymerization of the cyclic-olefin, wherein
and further wherein R30 to R48 in chemical equation 5 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; and, m and n are integers greater than or equal to 0.
4. The resin for thermal imprint of claim 2 , containing greater than or equal to one additive.
5. The resin for thermal imprint of claim 4 , wherein the additive contains at least either one of an anti-oxidizing agent or a lubricant.
6. The resin for thermal imprint of claim 2 , wherein a resin containing a skeleton represented by chemical equation 3 is a copolymer of cyclic-olefin represented by a following chemical equation 6 and ethylene; and wherein
and further wherein R30 to R48 in chemical equation 6 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; and, m and n are integers greater than or equal to 0.
7. A thermal imprint method comprising:
pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 1 , thereby transferring a pattern of the mold.
8. A thermal imprint method comprising steps of:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 1 ; and
releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.
9. A thermal imprint method comprising:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 1 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
10. A method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin being used for producing a sheet or a film, and containing at least one of skeletons represented by a following chemical equation 7 or a following chemical equation 8 in a main chain, and wherein:
a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and
and further wherein R1 to R29 in chemical equations 7, 8 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and [M] in equation 1 represents a value of MFR at 260° C.
11. A method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin being used for producing a sheet or a film, and containing at least one of skeletons represented by a following chemical equation 9 or a following chemical equation 10 in a main chain, and wherein:
a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and
and further wherein R1 to R29 in chemical equations 9, 10 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and, [M] in equation 1 represents a value of MFR at 260° C.
12. A thermal imprint method comprising:
pressing a mold, which is heated to,less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 2 thereby transferring a pattern of the mold.
13. A thermal imprint method comprising steps of:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 2 ; and
releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.
14. A thermal imprint method comprising:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 2 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
15. A thermal imprint method comprising:
pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 3 thereby transferring a pattern of the mold.
16. A thermal imprint method comprising steps of:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 3 ; and
releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.
17. A thermal imprint method comprising:
pressing a mold against a sheet or a4 film comprising the resin for thermal imprint of claim 3 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
18. A thermal imprint method comprising:
pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 4 thereby transferring a pattern of the mold.
19. A thermal imprint method comprising steps of:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 4 ; and
releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.
20. A thermal imprint method comprising:
pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 4 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.
Applications Claiming Priority (3)
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JP2005-357014 | 2005-09-12 | ||
JP2005357014 | 2005-12-09 | ||
PCT/JP2006/324423 WO2007066712A1 (en) | 2005-12-09 | 2006-12-07 | Resin for thermal imprinting |
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PCT/JP2006/324423 A-371-Of-International WO2007066712A1 (en) | 2005-12-09 | 2006-12-07 | Resin for thermal imprinting |
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US14/449,661 Continuation US9242407B2 (en) | 2005-12-09 | 2014-08-01 | Resin for thermal imprinting |
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US20100019410A1 true US20100019410A1 (en) | 2010-01-28 |
Family
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Family Applications (2)
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US12/086,165 Abandoned US20100019410A1 (en) | 2005-12-09 | 2006-07-12 | Resin for Thermal Imprinting |
US14/449,661 Expired - Fee Related US9242407B2 (en) | 2005-12-09 | 2014-08-01 | Resin for thermal imprinting |
Family Applications After (1)
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US14/449,661 Expired - Fee Related US9242407B2 (en) | 2005-12-09 | 2014-08-01 | Resin for thermal imprinting |
Country Status (6)
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US (2) | US20100019410A1 (en) |
EP (1) | EP1958970B1 (en) |
JP (1) | JP5331341B2 (en) |
KR (1) | KR101270114B1 (en) |
TW (1) | TWI473826B (en) |
WO (1) | WO2007066712A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100189985A1 (en) * | 2007-07-04 | 2010-07-29 | Maruzen Petrochemical Co., Ltd. | Thermal-imprinting resin, thermal-imprinting-resin solution, thermal-imprinting injection-molded body, thermal-imprinting thin film and production method thereof |
US20100310830A1 (en) * | 2007-11-14 | 2010-12-09 | Maruzen Petrochemical Co., Ltd. | Etching Mask, Base Material Having Etching Mask, Finely Processed Article, And Method For Production Of Finely Processed Article |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1930349B1 (en) * | 2005-09-27 | 2014-01-15 | Scivax Corporation | Resin for thermal imprint |
JP5394619B2 (en) * | 2007-07-04 | 2014-01-22 | 丸善石油化学株式会社 | Thermal imprint method |
TWI408041B (en) * | 2008-09-03 | 2013-09-11 | Univ Nat Sun Yat Sen | A manufacturing method for mold to produce brightness enhancement films |
JPWO2011090139A1 (en) * | 2010-01-21 | 2013-05-23 | Jsr株式会社 | Resin molded body |
JP2021037709A (en) * | 2019-09-04 | 2021-03-11 | 住友ベークライト株式会社 | Manufacturing method for molded product |
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- 2006-12-07 JP JP2007549169A patent/JP5331341B2/en not_active Expired - Fee Related
- 2006-12-07 EP EP06834178A patent/EP1958970B1/en not_active Not-in-force
- 2006-12-07 WO PCT/JP2006/324423 patent/WO2007066712A1/en active Application Filing
- 2006-12-08 TW TW95145979A patent/TWI473826B/en not_active IP Right Cessation
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2008
- 2008-05-30 KR KR1020087013143A patent/KR101270114B1/en not_active IP Right Cessation
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2014
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US20100189985A1 (en) * | 2007-07-04 | 2010-07-29 | Maruzen Petrochemical Co., Ltd. | Thermal-imprinting resin, thermal-imprinting-resin solution, thermal-imprinting injection-molded body, thermal-imprinting thin film and production method thereof |
US20100310830A1 (en) * | 2007-11-14 | 2010-12-09 | Maruzen Petrochemical Co., Ltd. | Etching Mask, Base Material Having Etching Mask, Finely Processed Article, And Method For Production Of Finely Processed Article |
US8597769B2 (en) * | 2007-11-14 | 2013-12-03 | Maruzen Petrochemical Co. Ltd. | Etching mask, base material having etching mask, finely processed article, and method for production of finely processed article |
Also Published As
Publication number | Publication date |
---|---|
EP1958970A1 (en) | 2008-08-20 |
KR101270114B1 (en) | 2013-05-31 |
EP1958970A4 (en) | 2009-07-01 |
JP5331341B2 (en) | 2013-10-30 |
US20140339735A1 (en) | 2014-11-20 |
TW200728331A (en) | 2007-08-01 |
US9242407B2 (en) | 2016-01-26 |
KR20080089338A (en) | 2008-10-06 |
JPWO2007066712A1 (en) | 2009-05-21 |
TWI473826B (en) | 2015-02-21 |
EP1958970B1 (en) | 2011-11-23 |
WO2007066712A1 (en) | 2007-06-14 |
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Owner name: SCIVAX CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TAKEMORI, TOSHIFUMI;TAKAYA, YOSHIAKI;MITA, TAKAHITO;AND OTHERS;REEL/FRAME:021162/0056;SIGNING DATES FROM 20080509 TO 20080529 Owner name: MARUZEN PETROCHEMICAL CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TAKEMORI, TOSHIFUMI;TAKAYA, YOSHIAKI;MITA, TAKAHITO;AND OTHERS;REEL/FRAME:021162/0056;SIGNING DATES FROM 20080509 TO 20080529 |
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STCB | Information on status: application discontinuation |
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