WO2011049097A1 - インプリント用モールド、その製造方法、インプリント装置およびインプリント方法 - Google Patents
インプリント用モールド、その製造方法、インプリント装置およびインプリント方法 Download PDFInfo
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- WO2011049097A1 WO2011049097A1 PCT/JP2010/068404 JP2010068404W WO2011049097A1 WO 2011049097 A1 WO2011049097 A1 WO 2011049097A1 JP 2010068404 W JP2010068404 W JP 2010068404W WO 2011049097 A1 WO2011049097 A1 WO 2011049097A1
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- WIPO (PCT)
- Prior art keywords
- mold
- imprint
- photocurable composition
- endless belt
- fine pattern
- Prior art date
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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
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/30—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
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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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
- B29C66/1122—Single lap to lap joints, i.e. overlap joints
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/114—Single butt joints
- B29C66/1142—Single butt to butt joints
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/14—Particular design of joint configurations particular design of the joint cross-sections the joint having the same thickness as the thickness of the parts to be joined
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/43—Joining a relatively small portion of the surface of said articles
- B29C66/432—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms
- B29C66/4322—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms by joining a single sheet to itself
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/43—Joining a relatively small portion of the surface of said articles
- B29C66/432—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms
- B29C66/4324—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms for making closed loops, e.g. belts
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
- B29C66/832—Reciprocating joining or pressing tools
- B29C66/8322—Joining or pressing tools reciprocating along one axis
- B29C66/83221—Joining or pressing tools reciprocating along one axis cooperating reciprocating tools, each tool reciprocating along one axis
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
- B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
- B29C66/91421—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the joining tools
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
- B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
- B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
- B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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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
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
- B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
- B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
- B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
- B29C66/91933—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion temperature
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
- B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
- B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
- B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
- B29C66/91943—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined higher than said glass transition temperature
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/92—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools
- B29C66/929—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools characterized by specific pressure, force, mechanical power or displacement values or ranges
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- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0072—Roughness, e.g. anti-slip
- B29K2995/0074—Roughness, e.g. anti-slip patterned, grained
Definitions
- the present invention relates to a resin-made endless belt-shaped imprint mold, a manufacturing method thereof, an imprint apparatus using the imprint mold, and an imprint method.
- a photocurable composition in which a mold having a reverse pattern of the fine pattern is applied to the surface of a substrate is used.
- radiation ultraviolet rays, etc.
- the reversal pattern of the mold is transferred to the surface of the substrate to form a fine pattern.
- imprint method for forming is known.
- the so-called nanoimprint method using a mold having a nano-order reversal pattern on the surface is attracting attention because it can form a fine pattern with a simple apparatus and in a short time compared to conventional methods using lithography and etching. Yes.
- the mold used for the imprint method is very expensive.
- a mold having a micron-order reversal pattern on the surface is usually manufactured by cutting the surface of a metal roll with a diamond bite, but the processing requires extremely high accuracy and a long time. It costs several million to tens of millions of yen (see paragraph [0005] of Patent Document 1). It is virtually impossible to form a nano-order reversal pattern on the surface of a metal roll by cutting, and it is usually an electron used in the manufacturing process of semiconductor elements on the surface of a quartz substrate, silicon substrate, etc.
- the inversion pattern must be formed by a method combining line drawing and etching, a method combining lithography and etching, or the like.
- the price of a mold having a nano-order reversal pattern on the surface exceeds, for example, 100 mm ⁇ 100 mm and exceeds 10 million yen. Moreover, since it takes time to form the reverse pattern in any mold, it is difficult to increase the area.
- the present invention relates to an imprint mold in which end portions of a resin film having a fine pattern formed on a surface thereof are joined to form an endless belt, and an imprint mold in which a step generated in a joined portion is reduced and the mold
- an imprint mold in which a step generated in a joined portion is reduced and the mold
- Provided are a production method, and an imprint apparatus and imprint method capable of suppressing the remaining of an uncured photocurable composition caused by a step at a joining portion of an endless belt-like imprint mold.
- the imprint mold of the present invention is characterized in that it is fused and joined in a state where the end portions of one or more resin films having a fine pattern on the surface are abutted to each other to form an endless belt.
- the fine pattern preferably has a plurality of convex portions and / or concave portions, and the pitch of the convex portions and / or concave portions is preferably 1 nm to 10 ⁇ m on average.
- the end portions of the resin film are abutted and fused together, and the difference between the maximum value and the minimum value of the mold thickness in the 10 mm width portion with the bonded joint line as the center line. Is preferably 20 ⁇ m or less.
- the imprint mold manufacturing method of the present invention is a method of manufacturing the imprint mold of the present invention, wherein the reversal pattern of the master mold having the reversal pattern of the fine pattern on the surface is one or a plurality of reversal patterns.
- a step of fusing and joining them to form an endless belt is a method of manufacturing the imprint mold of the present invention, wherein the reversal pattern of the master mold having the reversal pattern of the fine pattern on the surface is one or a plurality of reversal patterns.
- the reverse pattern preferably has a plurality of concave portions and / or convex portions corresponding to the convex portions and / or concave portions of the fine pattern, and the pitch of the concave portions and / or convex portions is preferably 1 nm to 10 ⁇ m on average.
- the imprint apparatus of the present invention includes a coating unit that applies a photocurable composition to the surface of a moving substrate, and a plurality of rolls that are in contact with the photocurable composition applied to the surface of the substrate.
- An endless belt-shaped mold that is laid and rotated, and light irradiation means for irradiating light to the photocurable composition in a state where the mold is in contact with the photocurable composition, and the endless belt
- the shaped mold is the imprint mold of the present invention.
- the imprint apparatus of the present invention includes an endless belt-shaped mold that is rolled around a plurality of rolls, an application unit that applies a photocurable composition to the surface of the mold, and a surface of a moving substrate. And a light irradiating means for irradiating the photocurable composition with light in a state where the photocurable composition applied to the surface of the mold is in contact with the mold. It is the mold for imprint of this.
- a photocurable composition is applied to the surface of a moving substrate, and the photocurable composition applied to the surface of the substrate is spread over a plurality of rolls.
- the imprint mold of the present invention is used as the mold.
- the imprint method of the present invention includes a step of applying a photocurable composition to the surface of an endless belt-shaped mold that is rolled around a plurality of rolls, and the photocuring applied to the surface of the mold.
- a step of bringing a moving substrate into contact with the curable composition; and a step of irradiating the photocurable composition with light in a state where the substrate is in contact with the photocurable composition The imprint mold of the present invention is used as a belt-shaped mold.
- the imprint mold of the present invention is an imprint mold in which the end portions of the resin film having a fine pattern formed on the surface thereof are fused and joined to form an endless belt, and the joining portion The difference in level is reduced.
- the imprint mold is formed by fusing and joining the end portions of the resin film having a fine pattern formed on the surface thereof to join each other to form an endless belt.
- the imprint apparatus of the present invention it is possible to suppress the remaining of the uncured photocurable composition caused by the step of the joining portion of the endless belt-like imprint mold.
- the imprinting method of the present invention it is possible to suppress the remaining of the uncured photocurable composition caused by the level difference of the joining portion of the endless belt-like imprinting mold.
- the application to the part that contacts the stepped part may be interrupted, but in the present invention, there is a step in the mold. Therefore, there is no need to apply intermittently to the substrate, and productivity is good.
- the application means may be retracted (separated) from the mold, but in the present invention, there is no step in the mold. Therefore, the pitch between the coating means and the mold can be always kept constant, and the productivity is good.
- FIG. 1 is a schematic diagram illustrating a first embodiment of an imprint apparatus according to the present invention. It is the schematic which shows 2nd Embodiment of the imprint apparatus of this invention. It is the schematic which shows 3rd Embodiment of the imprint apparatus of this invention.
- the imprint mold of the present invention is fused endlessly so that the ends of one or more resin films having a fine pattern on the surface face each other, so that the surface on the side having the fine pattern becomes an outer peripheral surface. It is a belt.
- the fine pattern has a plurality of convex portions and / or concave portions.
- a convex part the elongate protruding item
- a recessed part the elongate groove
- Examples of the shape of the ridge or groove include a straight line, a curved line, a bent shape, and the like. A plurality of ridges or grooves may exist in parallel and have a stripe shape. Examples of the cross-sectional shape of the ridge or groove in the direction perpendicular to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle. Examples of the shape of the protrusion or hole include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.
- the average width of the ridges or grooves is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the width of the ridge means the length of the base in the cross section in the direction orthogonal to the longitudinal direction.
- the width of the groove means the length of the upper side in the cross section in the direction orthogonal to the longitudinal direction.
- the average width of the protrusions or holes is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the width of the protrusion means the length of the bottom side in a cross section perpendicular to the longitudinal direction when the bottom surface is elongated, and otherwise means the maximum length of the bottom surface of the protrusion.
- the width of the hole means the length of the upper side in the cross section perpendicular to the longitudinal direction when the opening is elongated, and otherwise means the maximum length of the opening of the hole.
- the average height of the protrusions is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the average depth of the recesses is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the minimum dimension of the convex portion is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the minimum dimension means the minimum dimension among the width, length, and height of the convex portion.
- the minimum dimension of the recess is preferably 1 nm to 10 ⁇ m, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the minimum dimension means the minimum dimension among the width, length and depth of the recess.
- the pitch of the convex portions or concave portions is preferably 1 nm to 10 ⁇ m on average, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the pitch of a convex part means the distance from the center of a convex part (in the case of a convex strip, the center of a cross-sectional width direction) to the center of an adjacent convex part.
- the pitch of the recess means the distance from the center of the recess (in the case of a groove, the center in the cross-sectional width direction) to the center of the adjacent recess.
- the imprint mold of the present invention has the pitch in the above-mentioned range, that is, when it has a nano-order fine pattern, the imprint mold can maximize the effects of cost reduction and area increase. It is particularly useful as a molding mold.
- the resin film material examples include fluorine resin, silicone resin, acrylic resin, polycarbonate resin, polyester resin (polyethylene terephthalate, etc.), polyimide resin, polypropylene resin, polyethylene resin, nylon resin, polyphenylene sulfide resin, and cyclic polyolefin resin.
- a suitable resin film is selected according to the fusion method and the fusion conditions in a state where the end portions of the resin films are butted together.
- a surface-treated resin film may be used in order to enhance the adhesion with the photocurable composition used when the reverse pattern of the master mold is transferred to form a fine pattern.
- the surface treatment include primer coating treatment, ozone treatment, plasma etching treatment, and the like.
- the primer include polymethyl methacrylate, silane coupling agent, silazane and the like.
- a backing film such as a metal tape with adhesive, foil (aluminum tape, aluminum foil, etc.), a plastic film with adhesive, etc. It may be.
- a step is not generated on the outer peripheral surface side of the imprint mold at the joint portion of the backing film.
- the surface having the fine pattern may be treated with a release agent.
- the mold release agent include the following. Fluorine-based release agent: Zonyl TC coat (manufactured by DuPont), OPTOOL DSX, OPTOOL HD2100 (manufactured by Daikin Industries), Durasurf HD-2101Z (manufactured by Daikin Industries), Cytop CTL-107M (manufactured by Asahi Glass), Cytop CTL-107A (Asahi Glass Co., Ltd.), Novec EGC-1720 (manufactured by 3M Corporation), etc.
- Organic release agent silicone resin (dimethylsilicone oil KF96 (manufactured by Shin-Etsu Silicone), etc.), alkane resin (SAMLAY (manufactured by Nippon Soda Co., Ltd.) that forms an alkyl monomolecular film), etc.
- the imprint mold of the present invention because it is an endless belt that is fused in a state in which the ends of one or more resin films having a fine pattern on the surface are butted together, Even if there is almost no level difference in the joining portion or there is a level difference, the difference is slight compared with the case where the ends of the resin film are fused in a superimposed state.
- the method for producing an imprint mold of the present invention is a method having the following steps (I) to (II).
- (I) A step of transferring a reverse pattern of the master mold to the surface of the resin film to obtain a resin film having a fine pattern formed on the surface.
- (II) The process of making it an endless belt form so that the surface of the side which has a fine pattern may become an outer peripheral surface by fuse
- Step (I) Step (I) will be specifically described below.
- the imprint method optical imprint method or thermal imprint method
- the reverse pattern is efficiently and accurately transferred.
- the photoimprint method is particularly preferable because it can be performed.
- Specific examples of the method for forming a fine pattern by the photoimprint method include a method having the following steps (i) to (iv).
- (Iii) Light in a state where the master mold is pressed against the photocurable composition specifically, radiation such as ultraviolet light, visible light, or electron beam, etc.
- ultraviolet light, visible light, or electron beam These are collectively referred to as light, including radiation such as, etc.
- light including radiation such as, etc.
- a step of separating the resin film and the master mold Specific examples of the method for forming a fine pattern by the thermal imprint method include the following two types of steps. The first is a method having the following steps (i) to (iv).
- Ii) A step of pressing the master mold against the softened thermoplastic resin film so that the reverse pattern is in contact with the thermoplastic resin film.
- thermoplastic resin film A step of cooling the master mold while pressed against the softened thermoplastic resin film to cure the thermoplastic resin film and forming a fine pattern corresponding to the reverse pattern on the surface of the thermoplastic resin film.
- steps (i) to (iv) are continuously performed while moving the belt-shaped resin film and rotating the metal roll.
- steps (i) to (iv) are repeated a plurality of times.
- Master mold Materials for the master mold include quartz, glass, resin (polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, transparent fluororesin, etc.), silicon, metal (nickel, copper, stainless steel, titanium, etc.), SiC, mica, etc. Can be mentioned.
- the reverse pattern of the master mold is a reverse pattern corresponding to the fine pattern on the surface of the resin film.
- the reverse pattern has a plurality of concave portions and / or convex portions corresponding to the convex portions and / or concave portions of the fine pattern.
- the pitch of the recesses or projections is preferably 1 nm to 10 ⁇ m on average, more preferably 20 to 1000 nm, and particularly preferably 30 to 600 nm.
- the method for producing an imprint mold of the present invention is the case where the pitch is in the above-described range, that is, in the case of producing a resin-made endless belt-like imprint mold using a master mold having a nano-order reversal pattern. Since the effects of cost reduction and area increase of the printing mold can be maximized, it is particularly useful as a method for producing a nanoimprinting mold.
- Examples of the method for forming the reverse pattern on the surface of the master mold include a method combining electron beam drawing and etching, a method combining lithography and etching, and the like.
- a replica mold may be prepared from the master mold by nickel electroforming or the like, and the replica mold may be used as the master mold.
- thermoplastic resin film examples include fluorine resin, silicone resin, acrylic resin, polycarbonate resin, polyester resin (polyethylene terephthalate, etc.), polyimide resin, polypropylene resin, polyethylene resin, nylon resin, polyphenylene sulfide resin, and cyclic polyolefin resin. .
- Step (II) Step (II) will be specifically described below.
- the present invention is characterized in that an endless belt-like imprint mold 10 is formed by fusing and joining the end portions of the resin film 12 in a state where the end portions are butted together.
- an endless belt-like imprint mold 10 is formed by fusing and joining the end portions of the resin film 12 in a state where the end portions are butted together.
- the resin film is joined in a vertical direction with a pair of heated heaters 14 in the vicinity of the ends of the resin film 12 in a state where the ends of the resin film 12 face each other. And a method of pressure welding.
- the heating temperature of the heater 14 is preferably equal to or higher than the glass transition temperature or melting point of the resin film 12.
- the pressure applied by the heater 14 is preferably 0.1 MPa (gauge pressure) to 10 MPa (gauge pressure).
- the gap between the end portions when the end portions of the resin film are abutted may be in a state where there is no gap or may be in a state where there is a slight gap.
- the width of the gap is preferably 0.1 mm or less.
- the end portions of one or more resin films having a fine pattern on the surface are fused and joined together to form an endless belt. Therefore, it is possible to manufacture an imprint mold with little or no difference in the level of the joining portion.
- the imprint apparatus of the present invention includes a coating unit that applies a photocurable composition to the surface of a moving substrate, and a plurality of rolls that are in contact with the photocurable composition applied to the surface of the substrate.
- An endless belt-shaped mold that is laid and rotated, and a light irradiation unit that irradiates light to the photocurable composition in a state where the mold is in contact with the photocurable composition.
- the imprint apparatus of the present invention includes an endless belt-shaped mold that is rolled around a plurality of rolls, an application unit that applies a photocurable composition to the surface of the mold, and a surface of a moving substrate. And a light irradiating means for irradiating the photocurable composition with light in a state where the photocurable composition applied to the surface of the mold is in contact.
- the endless belt-shaped mold is fused and joined in a state where the end portions of one or more resin films having the fine pattern on the surface are abutted to each other. It is characterized in that it is an imprint mold of the present invention.
- an imprint apparatus according to the present invention will be described.
- FIG. 3 is a schematic view showing a first embodiment of the imprint apparatus of the present invention.
- the imprint apparatus includes an application means 22 for applying a photocurable composition to the surface of a belt-like substrate 20 that moves along each roll; an endless belt-like imprint that is stretched between a large roll 24 and a small roll 26.
- the mold 10 for printing in the state where the imprint mold 10 is in contact with the photocurable composition applied to the surface of the substrate 20 on the lower half surface of the large roll 24, the light is applied to the photocurable composition.
- the imprint mold 10 is an imprint mold according to the present invention, which is fused in an endless belt shape with the ends of one or more resin films having a fine pattern on the surface thereof butted together. .
- Examples of the coating means 22 include a die coater, a roll coater, a gravure coater, an ink jet coater, a spray coater, a spin coater, a flow coater, a blade coater, and a dip coater.
- the coating means 22 in the illustrated example is a die coater.
- Examples of the light irradiation means 28 include a high pressure mercury lamp, an ultra high pressure mercury lamp, a low pressure mercury lamp, an ultraviolet fluorescent lamp, a xenon lamp, a carbon arc lamp, an ultraviolet LED lamp, a visible light fluorescent lamp, a visible light incandescent lamp, and a visible light LED lamp. It is done.
- the large roll 24 and the small roll 26 are rotated in the same direction, so that the imprint mold 10 moves in the same direction as the movement direction of the substrate 20 on the lower half surface of the large roll 24.
- the mold 10 is rotated.
- the nip roll 32 and the peeling roll 34 are arranged so as to sandwich the large roll 24, so that the substrate 20 pressed against the imprint mold 10 on the surface of the large roll 24 by the nip roll 32 is placed under the large roll 24. It moves with the mold 10 for imprinting along the half surface.
- FIG. 4 is a schematic view showing a second embodiment of the imprint apparatus of the present invention.
- symbol is attached
- the imprinting apparatus is stretched over the application means 22 for applying the photocurable composition to the surface of the belt-like substrate 20 that moves along each roll; the upstream roll 36, the downstream roll 38, and the cooling roll 40.
- the light irradiation roll 42 is a glass roll provided with light irradiation means inside.
- the lower part of the light irradiation roll 42 is the highest of the upstream roll 36 so that the contact area between the photocurable composition applied to the surface of the substrate 20 and the imprint mold 10 is increased. It arrange
- the upstream roll 36, the downstream roll 38, and the cooling roll 40 rotate in the same direction so that the imprint mold 10 moves between the upstream roll 36 and the downstream roll 38 in the moving direction of the substrate 20.
- the imprint mold 10 is rotated so as to move in the same direction.
- the cooling roll 40 cools the imprint mold 10 heated by light irradiation.
- FIG. 5 is a schematic view showing a third embodiment of the imprint apparatus of the present invention.
- the imprint apparatus includes an endless belt-like imprint mold 10 that is stretched over three rolls of an upper roll 46, an upstream lower roll 48, and a downstream lower roll 50 that are arranged at the apex of a substantially equilateral triangle; A coating means 22 that is disposed opposite to the upper roll 46 via the printing mold 10 and applies the photocurable composition to the surface of the imprinting mold 10; and between the upstream lower roll 48 and the downstream lower roll 50.
- the upper roll 46, the upstream side lower roll 48, and the downstream side lower roll 50 rotate in the same direction, so that the imprint mold 10 is a base material between the upstream side lower roll 48 and the downstream side lower roll 50.
- the imprint mold 10 is rotated so as to move in the same direction as the movement direction of 20.
- the endless belt-shaped mold is the imprint mold of the present invention in which the level difference generated at the joint portion is reduced
- the imprint mold is photocurable.
- the composition is brought into contact with the composition, less air is left in the joining portion, and the curing of the photocurable composition in the portion is less likely to be hindered.
- it is possible to suppress the remaining of the uncured photocurable composition caused by the level difference of the joining portion of the endless belt-like imprint mold.
- the imprint apparatus according to the present invention is not limited to the illustrated embodiment.
- the effect of this invention can be show
- the imprint method of the present invention is a method having the following steps (a) to (d).
- the imprint method of the present invention is a method having the following steps (a ′) to (d ′).
- a ' The process of apply
- B ′ A step of bringing the moving base material into contact with the photocurable composition applied to the surface of the mold.
- C ′ In a state where the substrate is in contact with the photocurable composition, the photocurable composition is irradiated with light to cure the photocurable composition, and a reverse pattern corresponding to the fine pattern of the mold is used as a basis. Forming on the surface of the material.
- D ′ A step of separating the substrate and the mold.
- the imprint method of the present invention as an endless belt-shaped mold, the above-described one or more resin films having a fine pattern on the surface are fused in a state where the end portions are butted to form an endless belt shape.
- the present invention is characterized by using the imprint mold of the present invention.
- the imprint mold it is preferable to use a mold in which the maximum step at the joint portion of the mold is lower than the film thickness of the photocurable composition applied to the surface of the substrate. If the difference in level of the bonded portion is lower than the film thickness of the photocurable composition, the level difference in the bonded portion can be absorbed by the photocurable composition applied to the surface of the base material. The air that is buried and left in the joining portion is reduced, and the curing of the photocurable composition in the portion is hardly inhibited. As a result, it is possible to suppress the remaining of the uncured photocurable composition caused by the level difference of the joining portion of the endless belt-like imprint mold.
- the maximum value and the minimum value of the thickness of the mold within an area of 1 mm square at the joint portion of the mold that is, a portion having a width of 10 mm centered on the butting position
- the difference is 20 ⁇ m or less regardless of the 1 mm square of the above portion.
- the end portions of the resin film are abutted and fused together, and the maximum value and the minimum value of the mold thickness in a portion having a width of 10 mm with the bonded joint line as the center line.
- the difference is preferably 20 ⁇ m or less.
- the difference is more preferably 15 ⁇ m or less, and further preferably 10 ⁇ m or less.
- the imprinting method of the present invention can be carried out, for example, by using a known imprinting device provided with an endless belt-like mold in addition to the imprinting devices of the first to third embodiments described above.
- Materials for the base material include resins (for example, fluorine resins, silicone resins, acrylic resins, polycarbonates, polyesters (polyethylene terephthalate, etc.), polyimides, polypropylenes, polyethylenes, nylon resins, polyphenylene sulfides, cyclic polyolefins, etc.), glass, metals, etc. Is mentioned.
- resins for example, fluorine resins, silicone resins, acrylic resins, polycarbonates, polyesters (polyethylene terephthalate, etc.), polyimides, polypropylenes, polyethylenes, nylon resins, polyphenylene sulfides, cyclic polyolefins, etc.
- a transparent resin base material is preferable as the base material because flexibility and light transmittance are required.
- a transparent resin base material is preferable as the base material because flexibility and light transmittance are required.
- a glass substrate can be used as the substrate.
- the photocurable composition used for the manufacturing method of the imprint mold May be the same or different.
- the coating method of the photocurable composition include an ink jet method, a potting method, a spin coating method, a casting method, a dip coating method, a Langmuir Projet method, a vacuum deposition method, etc. in addition to a die coating method and a roll coating method. It is done.
- the photocurable composition may be disposed on the entire surface of the substrate or may be disposed on a part of the surface of the substrate.
- the imprint mold of the present invention since the imprint mold of the present invention in which the level difference generated at the joint portion is reduced is used as the endless belt-shaped mold, the imprint mold is optically When the curable composition is brought into contact with the curable composition, less air is left in the bonded portion, and the curing of the photocurable composition at the portion is less likely to be inhibited. As a result, it is possible to suppress the remaining of the uncured photocurable composition caused by the level difference of the joining portion of the endless belt-like imprint mold.
- an article having a fine pattern on its surface can be produced.
- the article having a fine pattern on the surface include the following articles.
- Optical elements microlens arrays, optical waveguide elements, optical switching elements (grid polarization elements, wave plates, etc.), Fresnel zone plate elements, binary elements, blaze elements, photonic crystals, etc.
- Antireflection member AR (Anti Reflection) coating member or the like.
- Chips Biochip, ⁇ -TAS (Micro-Total Analysis Systems) chip, microreactor chip, etc.
- Example 1 (Preparation of photocurable composition) To a 1000 mL four-necked flask equipped with a stirrer and a condenser, 60 g of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DPH), 40 g of neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-NPG), 4.0 g of photopolymerization initiator (manufactured by Ciba Specialty Chemicals, IRGACURE907), Fluorine-containing surfactant (manufactured by Asahi Glass Co., Ltd., co-oligomer of fluoroacrylate (CH 2 ⁇ CHCOO (CH 2 ) 2 (CF 2 ) 8 F) and butyl acrylate), fluorine content: about 30% by mass, mass average mole
- the flask was homogenized by stirring for 1 hour in a state of normal temperature and light shielding. Next, 100 g (solid content: 30 g) of colloidal silica was slowly added while stirring the flask, and the mixture was stirred and homogenized for 1 hour at room temperature and in the light-shielded state. Next, 340 g of cyclohexanone was added, and the mixture was stirred for 1 hour with the inside of the flask at room temperature and light-shielded to obtain a photocurable composition (1).
- a quartz mold (area: 150 mm ⁇ 150 mm, pattern area: 100 mm ⁇ 100 mm, groove pitch: 160 nm) in which a plurality of grooves are formed in parallel with each other at a predetermined pitch through flat portions formed between the grooves. , Groove width: 65 nm, groove depth: 200 nm, groove length: 100 mm, groove cross-sectional shape: substantially isosceles triangle).
- a nickel master mold (area: 150 mm ⁇ 150 mm) in which a plurality of ridges are formed in parallel with each other at a predetermined pitch through flat portions formed between the ridges by nickel electroforming from the quartz mold.
- Pattern area 100 mm ⁇ 100 mm, pitch of ridges: 160 nm, width of bottom of ridges: 65 nm, height of ridges: 200 nm, length of ridges: 100 mm, cross-sectional shape of ridges: approximately isosceles triangle ).
- the ultraviolet ray of energy (1000 mJ) is irradiated for 15 seconds to cure the photocurable composition (1), and a plurality of grooves corresponding to the ridges of the nickel master mold and flat portions between the grooves are part of the surface.
- a PET film (groove pitch: 160 nm, groove width: 65 nm, groove depth: 200 nm) was obtained.
- Fluorine-based release agent (Daikin Kogyo Co., Ltd., OPTOOL DSX) was dissolved in a fluorine-based solvent (Asahi Glass Co., Ltd., CT-Solv.100) to form a release agent solution (1) (concentration of fluorine-based compound: 0. 1% by mass) was prepared.
- the resin film (1) is dipped into the release agent solution (1), pulled up, immediately rinsed with a fluorine-based solvent (Asahi Glass Co., Ltd., CT-Solv.100), and maintained at 60 ° C. and 90% RH at constant temperature and high humidity. After curing in a bath for 1 hour, the surface of the resin film (1) was treated with a release agent.
- the endless belt-shaped imprint mold (1) was stretched over the large roll 24 and the small roll 26 of the imprint apparatus shown in FIG.
- the same PET film as described above having a thickness of 100 ⁇ m was used as the substrate 20
- the same photocurable composition (1) as described above was used as the photocurable composition
- the high-pressure mercury lamp was used as the light irradiation means 28.
- Imprinting was performed under the conditions of a moving speed of the substrate 20 of 1 m / min and a coating film thickness of 10 ⁇ m of the photocurable composition (1), and a reverse pattern corresponding to the fine pattern of the imprint mold (1) Of the bottom of the ridge: 65 nm, the height of the ridge: 200 nm, the length of the ridge: 100 mm, the cross-sectional shape of the ridge: approximately isosceles triangle) on the surface of the substrate 20, A light transmissive substrate of a wire grid type polarizer was obtained.
- the imprint mold of the present invention is useful as a mold for producing an optical member such as an antireflection member or a wire grid polarizer by an imprint method, particularly a nanoimprint method.
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Abstract
Description
前記微細パターンは、複数の凸部およびまたは凹部を有し、該凸部およびまたは凹部のピッチが、平均で1nm~10μmであることが好ましい。
また、前記微細パターンは、エンドレスベルト状にされた樹脂フィルムの外周面に有することが好ましい。
前記インプリント用モールドにおいては、樹脂フィルムの端部同士が突き合わされて融着され、接合された接合線を中心線とする10mmの幅の部分におけるモールドの厚さの最大値と最小値の差が20μm以下であることが好ましい。
前記反転パターンは、前記微細パターンの凸部およびまたは凹部に対応した複数の凹部およびまたは凸部を有し、該凹部およびまたは凸部のピッチが、平均で1nm~10μmであることが好ましい。
本発明のインプリント用モールドの製造方法によれば、微細パターンが表面に形成された樹脂フィルムの端部同士を突き合わせた状態で融着して接合してエンドレスベルト状にしたインプリント用モールドであって、接合部分に生じる段差が小さくされたインプリント用モールドを製造できる。
本発明のインプリント方法によれば、エンドレスベルト状のインプリント用モールドの接合部分の段差によって生じる未硬化の光硬化性組成物の残存を抑えることができる。
また、モールド側に光硬化性樹脂を塗布する場合、エンドレスベルト状のモールドに段差があると、塗布手段をモールドから退避させる(離す)ことがあるが、本発明においては、モールドに段差がないので、塗布手段とモールドとのピッチを常に一定にでき、生産性がよい。
本発明のインプリント用モールドは、微細パターンを表面に有する1枚以上の樹脂フィルムの端部同士を突き合わせた状態で融着して、微細パターンを有する側の表面が外周面となるようにエンドレスベルト状にしたものである。
微細パターンは、複数の凸部およびまたは凹部を有する。
凸部としては、樹脂フィルムの表面に延在する長尺の凸条、表面に点在する突起等が挙げられる。
凹部としては、樹脂フィルムの表面に延在する長尺の溝、表面に点在する孔等が挙げられる。
凸条または溝の、長手方向に直交する方向の断面形状としては、長方形、台形、三角形、半円形等が挙げられる。
突起または孔の形状としては、三角柱、四角柱、六角柱、円柱、三角錐、四角錐、六角錐、円錐、半球、多面体等が挙げられる。
突起または孔の幅は、平均で1nm~10μmが好ましく、20~1000nmがより好ましく、30~600nmが特に好ましい。突起の幅とは、底面が細長い場合、長手方向に直交する方向の断面における底辺の長さを意味し、そうでない場合、突起の底面における最大長さを意味する。孔の幅とは、開口部が細長い場合、長手方向に直交する方向の断面における上辺の長さを意味し、そうでない場合、孔の開口部における最大長さを意味する。
凹部の深さは、平均で1nm~10μmが好ましく、20~1000nmがより好ましく、30~600nmが特に好ましい。
凹部の最小寸法は、1nm~10μmが好ましく、20~1000nmがより好ましく、30~600nmが特に好ましい。最小寸法とは、凹部の幅、長さおよび深さのうち最小の寸法を意味する。
樹脂フィルムの材料としては、フッ素樹脂、シリコーン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂(ポリエチレンテレフタレート等)、ポリイミド樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ナイロン樹脂、ポリフェニレンサルファイド樹脂、環状ポリオレフィン樹脂等が挙げられる。具体的に使用される樹脂フィルムとしては、樹脂フィルムの端部同士を突き合わせた状態での融着方法、融着条件に応じて、適合する樹脂フィルムが選ばれる。
樹脂フィルムの裏面側には、インプリント用モールドの強度を向上させる点から、粘着剤付きの金属テープ、箔(アルミニウムテープ、アルミニウム箔等)、粘着剤付きのプラスチックフィルム等の裏打ちフィルムを貼り合わせていてもよい。かかる裏打ちフィルムによりエンドレスベルト状のインプリント用モールドの強度を向上させる場合には、裏打ちフィルムの接合部において、インプリント用モールドの外周面側に段差が生じないようにされる。
本発明のインプリント用モールドは、微細パターンを有する側の表面が離型剤によって処理されていてもよい。
離型剤としては、たとえば、下記のものが挙げられる。
フッ素系離型剤:ゾニールTCコート(デュポン社製)、オプツールDSX、オプツールHD2100(ダイキン工業社製)、デュラサーフHD-2101Z(ダイキン工業社製)、サイトップCTL-107M(旭硝子社製)、サイトップCTL-107A(旭硝子社製)、ノベックEGC-1720(3M社製)等。
有機物系離型剤:シリコーン系樹脂(ジメチルシリコーン系オイルKF96(信越シリコーン社製)等)、アルカン系樹脂(アルキル系単分子膜を形成するSAMLAY(日本曹達社製)等)等。
本発明のインプリント用モールドの製造方法は、下記の工程(I)~(II)を有する方法である。
(I)マスターモールドの反転パターンを樹脂フィルムの表面に転写して、微細パターンが表面に形成された樹脂フィルムを得る工程。
(II)微細パターンを表面に有する1枚以上の樹脂フィルムの端部同士を突き合わせた状態で融着して、微細パターンを有する側の表面が外周面となるようにエンドレスベルト状にする工程。
工程(I)について、以下に具体的に説明する。
(微細パターンの形成方法)
マスターモールドの反転パターンを樹脂フィルムの表面に転写して微細パターンを形成する方法としては、インプリント法(光インプリント法または熱インプリント法)が好ましく、反転パターンを効率よく、かつ精度よく転写できる点から、光インプリント法が特に好ましい。
(i)光硬化性組成物を樹脂フィルムの表面に塗布する工程。
(ii)マスターモールドを、反転パターンが光硬化性組成物に接するように、光硬化性組成物に押しつける工程。
(iii)マスターモールドを光硬化性組成物に押しつけた状態で光(具体的には、紫外線、可視光、あるいは電子線等の放射線など。本明細書においては、紫外線、可視光、あるいは電子線等の放射線などを含め、これらを光と総称する。)を照射して光硬化性組成物を硬化させて、反転パターンに対応する微細パターンを樹脂フィルムの表面に形成する工程。
(iv)樹脂フィルムとマスターモールドとを分離する工程。
熱インプリント法による微細パターンの形成方法としては、具体的には下記の2種類の工程が挙げられる。
1つ目は以下の工程(i)~(iv)を有する方法である。
(i)熱可塑性樹脂フィルムを加熱して軟化させる工程。
(ii)マスターモールドを、反転パターンが熱可塑性樹脂フィルムに接するように、軟化した熱可塑性樹脂フィルムに押しつける工程。
(iii)マスターモールドを軟化した熱可塑性樹脂フィルムに押しつけた状態で冷却して熱可塑性樹脂フィルムを硬化させて、反転パターンに対応する微細パターンを熱可塑性樹脂フィルムの表面に形成する工程。
(iv)熱可塑性樹脂フィルムとマスターモールドとを分離する工程。
2つ目は以下の工程(i)~(iv)を有する方法である。
(i)マスターモールドを加熱する工程。
(ii)加熱されたマスターモールドを、反転パターンが熱可塑性樹脂フィルムに接するように、熱可塑性樹脂フィルムに押しつける工程。
(iii)マスターモールドを熱可塑性樹脂フィルムに押しつけた状態で冷却して熱可塑性樹脂フィルムを硬化させて、反転パターンに対応する微細パターンを熱可塑性樹脂フィルムの表面に形成する工程。
(iv)熱可塑性樹脂フィルムとマスターモールドとを分離する工程。
マスターモールドが平板状の場合、工程(i)~(iv)は、複数回繰り返し行う。
マスターモールドの材料としては、石英、ガラス、樹脂(ポリジメチルシロキサン、環状ポリオレフィン、ポリカーボネート、ポリエチレンテレフタレート、透明フッ素樹脂等)、シリコン、金属(ニッケル、銅、ステンレス、チタン等)、SiC、マイカ等が挙げられる。
反転パターンは、微細パターンの凸部およびまたは凹部に対応した複数の凹部およびまたは凸部を有する。
凹部および凸部の各寸法は、上述の微細パターンにおける凸部および凹部の各寸法に対応する。
本発明のインプリント用モールドの製造方法は、ピッチが前記範囲である、すなわちナノオーダーの反転パターンを有するマスターモールドを用いて樹脂製のエンドレスベルト状のインプリント用モールドを製造する場合において、インプリント用モールドの低コスト化および大面積化の効果を最大限に発揮できるため、ナノインプリント用モールドの製造方法として特に有用である。
また、マスターモールドから、ニッケル電鋳等によって複製モールドを作製し、該複製モールドをマスターモールドとして用いてもよい。
光硬化性組成物としては、国際公開第2007/116972号パンフレットの明細書段落[0029]~[0074]に記載の光硬化性組成物等、公知の光硬化性組成物を用いることができる。
(熱可塑性樹脂フィルム)
熱可塑性樹脂フィルムとしては、フッ素樹脂、シリコーン樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂(ポリエチレンテレフタレート等)、ポリイミド樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ナイロン樹脂、ポリフェニレンサルファイド樹脂、環状ポリオレフィン樹脂等が挙げられる。
工程(II)について、以下に具体的に説明する。
(樹脂フィルムの接合方法)
本発明においては、図1に示すように、樹脂フィルム12の端部同士を突き合わせた状態で融着して接合し、エンドレスベルト状のインプリント用モールド10にすることに特徴がある。
樹脂フィルムの端部同士を突き合わせた状態で融着した場合は、図2に示すように、樹脂フィルム12の端部同士を重ね合わせた状態で融着した場合に比べ、接合部分の段差がほとんどない、または段差があってもわずかである。
ヒータ14の加熱温度は、樹脂フィルム12のガラス転移温度または融点以上が好ましい。
ヒータ14による加圧は、0.1MPa(ゲージ圧)~10MPa(ゲージ圧)が好ましい。
本発明のインプリント装置は、移動する基材の表面に光硬化性組成物を塗布する塗布手段と、前記基材の表面に塗布された前記光硬化性組成物に接触する、複数のロールに架け渡されて輪転するエンドレスベルト状のモールドと、前記光硬化性組成物に前記モールドが接触した状態で、前記光硬化性組成物に光を照射する光照射手段とを有する。
また、本発明のインプリント装置は、複数のロールに架け渡されて輪転するエンドレスベルト状のモールドと、前記モールドの表面に光硬化性組成物を塗布する塗布手段と、移動する基材の表面に、前記モールドの表面に塗布された光硬化性組成物が接触した状態で、前記光硬化性組成物に光を照射する光照射手段とを有する。
以下、本発明のインプリント装置の実施形態を説明する。
図3は、本発明のインプリント装置の第1の実施形態を示す概略図である。
インプリント装置は、各ロールに沿って移動する帯状の基材20の表面に光硬化性組成物を塗布する塗布手段22と;大ロール24および小ロール26に架け渡されたエンドレスベルト状のインプリント用モールド10と;大ロール24の下半分の表面にて、基材20の表面に塗布された光硬化性組成物にインプリント用モールド10が接触した状態で、光硬化性組成物に光を照射する光照射手段28と;基材20を介して塗布手段22に対向配置されたダイ下ロール30と;光硬化性組成物が塗布された基材20を、大ロール24の表面のインプリント用モールド10に押し付けるニップロール32と;大ロール24の表面のインプリント用モールド10から、微細パターンが表面に形成された基材20を剥離する剥離ロール34とを有して概略構成される。
光照射手段28としては、たとえば高圧水銀灯、超高圧水銀灯、低圧水銀灯、紫外線蛍光灯、キセノン灯、炭素アーク灯、紫外線LED灯、可視光蛍光灯、可視光白熱灯、可視光LED灯等が挙げられる。
また、ニップロール32および剥離ロール34は、大ロール24を挟むようにして配置されることによって、ニップロール32によって大ロール24の表面のインプリント用モールド10に押し付けられた基材20を、大ロール24の下半分の表面に沿って、インプリント用モールド10とともに移動させる。
図4は、本発明のインプリント装置の第2の実施形態を示す概略図である。第1の実施形態と同じ構成については、同じ符号を付して説明を省略する。
インプリント装置は、各ロールに沿って移動する帯状の基材20の表面に光硬化性組成物を塗布する塗布手段22と;上流側ロール36、下流側ロール38および冷却ロール40に架け渡されたエンドレスベルト状のインプリント用モールド10と;上流側ロール36と下流側ロール38との間にて、光硬化性組成物が塗布された基材20を表面に沿って移動させつつ、基材20の表面に塗布された光硬化性組成物をインプリント用モールド10に押し付けた状態で、光硬化性組成物に光を照射する光照射ロール42と;基材20を介して塗布手段22に対向配置されたダイ下ロール30と;光放射線照射ロール42から、インプリント用モールド10の微細パターンに対応する反転パターンが表面に形成された基材20を引き離すガイドロール44とを有して概略構成される。
光照射ロール42は、基材20の表面に塗布された光硬化性組成物とインプリント用モールド10との接触面積が大きくなるように、光照射ロール42の下部が上流側ロール36の最も高い点と下流側ロール38の最も高い点とを結ぶ線よりも下側に位置するように、配置される。
また、冷却ロール40は、光の照射によって加熱されたインプリント用モールド10を冷却するものである。
図5は、本発明のインプリント装置の第3の実施形態を示す概略図である。第1の実施形態と同じ構成については、同じ符号を付して説明を省略する。
インプリント装置は、略正三角形の頂点に配置された上ロール46、上流側下ロール48および下流側下ロール50の3つのロールに架け渡されたエンドレスベルト状のインプリント用モールド10と;インプリント用モールド10を介して上ロール46に対向配置され、インプリント用モールド10の表面に光硬化性組成物を塗布する塗布手段22と;上流側下ロール48と下流側下ロール50との間にて、各ロールに沿って移動する基材20に、インプリント用モールド10の表面に塗布された光硬化性組成物が接触した状態で、光硬化性組成物に光を照射する光照射手段28と;インプリント用モールド10よりも上流側にて基材20を支持する支持ロール52と;基材20を介して上流側下ロール48に対向配置された上流側ニップロール54と;基材20を介して下流側下ロール50に対向配置された下流側ニップロール56と;上流側下ロール48と下流側下ロール50との間にて、インプリント用モールド10を基材20の表面に塗布された光硬化性組成物に押し付ける3つの押し付けロール58とを有して概略構成される。
本発明のインプリント方法は、下記の工程(a)~(d)を有する方法である。
(a)移動する基材の表面に光硬化性組成物を塗布する工程。
(b)基材の表面に塗布された光硬化性組成物に、複数のロールに架け渡されて輪転するエンドレスベルト状のモールドを接触させる工程。
(c)光硬化性組成物にモールドが接触した状態で、光硬化性組成物に光を照射して光硬化性組成物を硬化させて、モールドの微細パターンに対応する反転パターンを基材の表面に形成する工程。
(d)基材とモールドとを分離する工程。
(a’)複数のロールに架け渡されて輪転するエンドレスベルト状のモールドの表面に光硬化性組成物を塗布する工程。
(b’)モールドの表面に塗布された光硬化性組成物に、移動する基材を接触させる工程。
(c’)光硬化性組成物に基材が接触した状態で、光硬化性組成物に光を照射して光硬化性組成物を硬化させて、モールドの微細パターンに対応する反転パターンを基材の表面に形成する工程。
(d’)基材とモールドとを分離する工程。
光硬化性組成物の塗布方法としては、ダイコート法、ロールコート法の他に、インクジェット法、ポッティング法、スピンコート法、キャスト法、ディップコート法、ラングミュラープロジェット法、真空蒸着法等が挙げられる。
光硬化性組成物は、基材の全面に配置してもよく、基材の表面の一部に配置してもよい。
本発明のインプリント装置およびインプリント方法によれば、微細パターンを表面に有する物品を製造できる。
微細パターンを表面に有する物品としては、下記の物品が挙げられる。
・光学素子:マイクロレンズアレイ、光導波路素子、光スイッチング素子(グリッド偏光素子、波長板等。)、フレネルゾーンプレート素子、バイナリー素子、ブレーズ素子、フォトニック結晶等。
・反射防止部材:AR(Anti Reflection)コート部材等。
・チップ類:バイオチップ、μ-TAS(Micro-Total Analysis Systems)用のチップ、マイクロリアクターチップ等。
・その他:記録メディア、ディスプレイ材料、触媒の担持体、フィルター、センサー部材、半導体(MEMSを含む。)、電解用のレプリカ等。
(光硬化性組成物の調製)
撹拌機および冷却管を装着した1000mLの4つ口フラスコに、
ジペンタエリスリトールヘキサアクリレート(新中村化学工業社製、NK エステル A-DPH)の60g、
ネオペンチルグリコールジアクリレート(新中村化学工業社製、NK エステル A-NPG)の40g、
光重合開始剤(チバスペシャリティーケミカルズ社製、IRGACURE907)の4.0g、
含フッ素界面活性剤(旭硝子社製、フルオロアクリレート(CH2=CHCOO(CH2)2(CF2)8F)とブチルアクリレートとのコオリゴマー、フッ素含有量:約30質量%、質量平均分子量:約3000)の0.1g、
重合禁止剤(和光純薬社製、Q1301)の1.0g、および
シクロヘキサノンの65.0gを入れた。
複数の溝が、該溝間に形成される平坦部を介して互いに平行にかつ所定のピッチで形成された石英製モールド(面積:150mm×150mm、パターン面積:100mm×100mm、溝のピッチ:160nm、溝の幅:65nm、溝の深さ:200nm、溝の長さ:100mm、溝の断面形状:略二等辺三角形)を用意した。
工程(i):
長さ150mm、幅150mm、厚さ100μmの高透過ポリエチレンテレフタレート(PET)フィルム(帝人デュポン社製、帝人テトロンO3)の表面に、光硬化性組成物(1)をスピンコート法により塗布し、厚さ5μmの光硬化性組成物(1)の塗膜を形成した。
工程(ii):
前記ニッケル製マスターモールドを、凸条が光硬化性組成物(1)の塗膜に接するように、25℃にて0.5MPa(ゲージ圧)で光硬化性組成物(1)の塗膜に押しつけた。
工程(ii)によって得られた状態を保持したまま、PETフィルム側から、照射の光として、高圧水銀灯(周波数:1.5kHz~2.0kHz、主波長光:255nm、315nmおよび365nm、365nmにおける照射エネルギー:1000mJ)の紫外線を15秒間照射し、光硬化性組成物(1)を硬化させて、ニッケル製マスターモールドの凸条に対応する複数の溝および該溝間の平坦部を表面の一部に有するPETフィルム(溝のピッチ:160nm、溝の幅:65nm、溝の深さ:200nm)を得た。
工程(iv):
PETフィルムからニッケル製マスターモールドをゆっくり分離した。
樹脂フィルム(1)を離型剤溶液(1)にディップし、引き上げた後、直ちにフッ素系溶媒(旭硝子社製、CT-Solv.100)でリンスし、60℃、90%RHの恒温高湿槽中にて1時間キュアし、樹脂フィルム(1)の表面に離型剤処理を施した。
離型剤処理した樹脂フィルム(1)の端部同士を突き合わせた状態で、突き合わせ部分を、250℃に加熱された幅10mmの一対のヒータで5MPa(ゲージ圧)で上下方向から挟み込み、加熱融着して接合し、エンドレスベルト状のインプリント用モールド(1)を得た。
接合部分の段差を、マイクロメータ(ミツトヨ社製)を用いて測定したところ、接合部分(突き合わせの位置を中心線とする10mmの幅の部分)において、1mm角の面積内のモールドの厚さの最大値と最小値との差が20μmを超える領域が存在しない。
エンドレスベルト状のインプリント用モールド(1)を、図3に示すインプリント装置の大ロール24および小ロール26に架け渡した。
基材20として厚さ100μmの前記と同様のPETフィルムを用い、光硬化性組成物として前記と同様の光硬化性組成物(1)を用い、光照射手段28として前記高圧水銀灯を用いた。
基材20の移動速度1m/分、光硬化性組成物(1)の塗布膜厚10μmの条件でインプリントを実施し、インプリント用モールド(1)の微細パターンに対応する反転パターン(凸条のピッチ:160nm、凸条の底部の幅:65nm、凸条の高さ:200nm、凸条の長さ:100mm、凸条の断面形状:略二等辺三角形)を基材20の表面に有する、ワイヤグリッド型偏光子の光透過性基板を得た。
なお、2009年10月21日に出願された日本特許出願2009-242392号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
12 樹脂フィルム
20 基材
22 塗布手段
24 大ロール
26 小ロール
28 放射線照射手段
36 上流側ロール
38 下流側ロール
40 冷却ロール
42 放射線照射ロール
46 上ロール
48 上流側下ロール
50 下流側下ロール
58 押し付けロール
Claims (10)
- 微細パターンを表面に有する1枚以上の樹脂フィルムを、その端部同士を突き合わせた状態で融着して接合し、エンドレスベルト状にした、インプリント用モールド。
- 前記微細パターンが、複数の凸部およびまたは凹部を有し、
該凸部およびまたは凹部のピッチが、平均で1nm~10μmである、請求項1に記載のインプリント用モールド。 - エンドレスベルト状にされた樹脂フィルムの外周面に微細パターンを有する、請求項1、または2に記載のインプリント用モールド。
- 請求項1~3のいずれか1項に記載のインプリント用モールドにおいて、樹脂フィルムの端部同士が突き合わされて融着され、接合された接合線を中心線とする10mmの幅の部分におけるモールドの厚さの最大値と最小値の差が20μm以下である、請求項1~3のいずれか1項に記載のインプリント用モールド。
- 請求項1~4のいずれか1項に記載のインプリント用モールドを製造する方法であって、
前記微細パターンの反転パターンを表面に有するマスターモールドの該反転パターンを樹脂フィルムの表面に転写して、微細パターンが表面に形成された樹脂フィルムを得る工程と、
微細パターンを表面に有する1枚以上の樹脂フィルムを、その端部同士を突き合わせた状態で融着して接合し、エンドレスベルト状にする工程と
を有する、インプリント用モールドの製造方法。 - 前記反転パターンが、前記微細パターンの凸部およびまたは凹部に対応した複数の凹部およびまたは凸部を有し、
該凹部およびまたは凸部のピッチが、平均で1nm~10μmである、請求項5に記載のインプリント用モールドの製造方法。 - 移動する基材の表面に光硬化性組成物を塗布する塗布手段と、
前記基材の表面に塗布された前記光硬化性組成物に接触する、複数のロールに架け渡されて輪転するエンドレスベルト状のモールドと、
前記光硬化性組成物に前記モールドが接触した状態で、前記光硬化性組成物に光を照射する光照射手段とを有し、
前記エンドレスベルト状のモールドが、請求項1~4のいずれか1項に記載のインプリント用モールドである、インプリント装置。 - 複数のロールに架け渡されて輪転するエンドレスベルト状のモールドと、
前記モールドの表面に光硬化性組成物を塗布する塗布手段と、
移動する基材の表面に、前記モールドの表面に塗布された光硬化性組成物が接触した状態で、前記光硬化性組成物に光を照射する光照射手段とを有し、
前記エンドレスベルト状のモールドが、請求項1~4のいずれか1項に記載のインプリント用モールドである、インプリント装置。 - 移動する基材の表面に光硬化性組成物を塗布する工程と、
前記基材の表面に塗布された前記光硬化性組成物に、複数のロールに架け渡されて輪転するエンドレスベルト状のモールドを接触させる工程と、
前記光硬化性組成物に前記モールドが接触した状態で、前記光硬化性組成物に光を照射する工程とを有し、
前記エンドレスベルト状のモールドとして、請求項1~4のいずれか1項に記載のインプリント用モールドを用いる、インプリント方法。 - 複数のロールに架け渡されて輪転するエンドレスベルト状のモールドの表面に光硬化性組成物を塗布する工程と、
前記モールドの表面に塗布された前記光硬化性組成物に、移動する基材を接触させる工程と、
前記光硬化性組成物に前記基材が接触した状態で、前記光硬化性組成物に光を照射する工程とを有し、
前記エンドレスベルト状のモールドとして、請求項1~4のいずれか1項に記載のインプリント用モールドを用いる、インプリント方法。
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JP2014080017A (ja) * | 2012-09-28 | 2014-05-08 | Soken Chem & Eng Co Ltd | 樹脂製モールドおよびその製造方法並びにその用途 |
WO2014080858A1 (ja) | 2012-11-22 | 2014-05-30 | 綜研化学株式会社 | インプリント用モールドの製造方法 |
WO2014080857A1 (ja) | 2012-11-22 | 2014-05-30 | 綜研化学株式会社 | インプリント用モールドの製造方法、インプリント用モールド、インプリント用モールド製造キット |
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JPWO2011049097A1 (ja) | 2013-03-14 |
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TWI501860B (zh) | 2015-10-01 |
CN102574327B (zh) | 2014-09-03 |
KR20120086687A (ko) | 2012-08-03 |
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