WO2016148118A1 - 凹凸パターン形成体の製造方法およびインプリント装置 - Google Patents
凹凸パターン形成体の製造方法およびインプリント装置 Download PDFInfo
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- WO2016148118A1 WO2016148118A1 PCT/JP2016/058060 JP2016058060W WO2016148118A1 WO 2016148118 A1 WO2016148118 A1 WO 2016148118A1 JP 2016058060 W JP2016058060 W JP 2016058060W WO 2016148118 A1 WO2016148118 A1 WO 2016148118A1
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- Prior art keywords
- roll
- resin layer
- film mold
- transferred
- mold
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- 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
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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
- B29C59/002—Component parts, details or accessories; Auxiliary operations
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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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- 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
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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
Definitions
- the present invention relates to a method for producing a concavo-convex pattern formed body and an apparatus used in the production method.
- the nanoimprint technology is a technique in which a mold having a concavo-convex pattern is pressed against a liquid resin on a substrate and the mold pattern is transferred to the resin.
- Concavo-convex patterns exist from nanoscales of 10 nm level to about 100 ⁇ m, and are used in various fields such as semiconductor materials, optical materials, storage media, micromachines, biotechnology, and the environment.
- a mold having a predetermined shape formed on the surface is pressed against a thermoplastic resin melted at a glass transition temperature or higher, the surface shape of the mold is thermally nanoimprinted on the thermoplastic resin, and the mold is cooled. And thermal nanoimprint for removing the mold, pressing the same mold against the photocurable resin, curing the photocurable resin with energy rays such as ultraviolet irradiation, and then removing the mold.
- FIG. 3 is a schematic diagram of a so-called plate-to-plate apparatus, which is an example of a conventional nanoimprint apparatus, that transfers the shape of a flat plate mold to a transfer target resin on a flat substrate.
- a plate-shaped mold fixed to the arm 101 is pressed against the transfer material resin layer applied to the flat substrate by moving the arm 101 downward, and imprinting is performed. After the layer was cured, the mold was peeled off from the cured transfer target resin layer by moving the arm 101 upward.
- the transfer operation and the curing operation of the transferred resin layer can be performed independently.
- the plate-shaped mold is pressed against the plate-shaped transferred resin layer, air bubbles are taken in between the mold and the transferred resin layer when pressed, and the resin cures as it is. It was difficult to accurately transfer the shape of the mold to the transferred resin layer.
- the mold and the cured transferred resin may be damaged.
- FIG. 4 is a schematic view of a so-called roll-to-roll apparatus that transfers the shape of a mold on a roll to a resin on the roll, which is an example of a further conventional nanoimprint apparatus.
- imprinting is performed by press-contacting a mold wound and fixed on a roll with a shape outside on a transferred resin layer on another roll.
- FIG. 5 is a schematic view of a so-called roll-to-plate type apparatus for transferring the shape of a mold on a roll to a resin on a flat substrate, which is an example of a further conventional nanoimprint apparatus.
- imprinting is performed by press-contacting a mold, which is wound and fixed on a roll with a shape outside, to a transfer material resin layer on a substrate.
- the mold is stuck and fixed to the roll, but there is a problem that a transfer defect occurs when foreign matter is mixed in the pasting surface or bubbles are bitten during the pasting. In that case, re-pasting was necessary.
- the mold is fixed to the roll with a strong adhesive, the mold once removed from the roll could not be reused.
- Patent Document 1 discloses an imprint mold fixing pressure-sensitive adhesive sheet for easily peeling a mold from a roll. Patent document 1 made it a subject that a mold does not peel from a roll in the case of imprint. Moreover, the mold was peeled off with the adhesive sheet.
- the mold contacts the transferred object only at the time of transfer, so the transfer operation to the transferred resin layer and the curing operation of the transferred resin layer are performed simultaneously. There was a need to do. Therefore, the mode of the imprint apparatus is limited, and the type of the transfer target resin is limited to the photocurable resin.
- Patent Document 2 describes an apparatus that separates a roll and a mold.
- this apparatus requires a large-scale configuration for raising and lowering the mold.
- the present invention does not capture air bubbles when the mold is brought into contact with the transferred resin layer, and the mold and the transferred transferred resin layer are damaged when the mold is peeled off from the transferred transferred resin layer. It is an object of the present invention to provide a method for producing a concavo-convex pattern forming body and an imprint apparatus.
- the present invention provides an imprint apparatus using a roll as a pressure application means, and a method for producing a concavo-convex pattern forming body and an imprint apparatus in which the mold can be easily attached to and detached from the roll and the mold once peeled from the roll can be reused
- the purpose is to provide.
- an object of the present invention is to provide a method for manufacturing a concavo-convex pattern forming body and an imprint apparatus that do not require simultaneous transfer operation and curing operation.
- the present invention relates to the following [1] to [4], for example.
- the transferred resin layer on which the concavo-convex pattern of the film mold is transferred by placing the roll on the transferred resin layer after curing and rotating the roll in the winding direction of the film mold;
- An imprint apparatus wherein the film mold is peeled off, and the film mold is wound up and collected on a roll surface.
- the mold can be peeled off from the roll during transfer and laminated on the transferred resin layer while using the roll as the pressure applying means, the transfer operation and the transferred resin layer can be performed. It is not necessary to perform the curing operation simultaneously.
- the peeled mold can be reused, it is possible to continuously manufacture the concavo-convex pattern formed body. Then, the mold laminated on the cured transfer material resin layer can be peeled off from the cured transfer material resin layer at a low peel angle with only a roll curvature, so that the mold and the cured transfer object are peeled off at the time of peeling. The transfer resin layer is not damaged.
- the imprint apparatus since the mold is transferred to the transfer material resin layer using a roll, no air bubbles are taken in between the mold and the transfer resin layer. Further, the imprint apparatus according to the present invention does not require a stamper to be attached to a support column or a rotating arm unlike a conventional roll-to-plate type apparatus, and thus can be reduced in size as compared with a conventional roll-to-plate type apparatus. It is.
- FIG. 1 is a schematic diagram showing the steps of a method for producing a concavo-convex pattern formed body of the present invention.
- FIG. 2 is a schematic view showing an indwelling means of the imprint apparatus used in the method for producing the concavo-convex pattern formed body of the present invention.
- FIG. 3 is a schematic diagram of a conventional plate-to-plate type imprint apparatus.
- FIG. 4 is a schematic diagram of a conventional roll-to-roll type imprint apparatus.
- FIG. 5 is a schematic view of a conventional roll-to-plate type imprint apparatus.
- the method for producing a concavo-convex pattern formed body of the present invention includes a step (1) of detachably winding and holding a film mold having a concavo-convex pattern on a surface on a roll having a locking capability on the surface, A step (2) of placing a substrate and a transferred body resin layer formed on the substrate on the surface, and a roll obtained in the step (1) on the surface of the transferred body resin layer.
- the roll is rotated while contacting the wound film mold, the film mold is peeled off from the roll and unwound onto the transfer resin layer, and the uneven pattern on the surface of the film mold is transferred to the transfer resin layer.
- Transferred resin layer (5) a step of rotating the surface of the film mold laminated on the surface while rotating a roll having a locking ability, peeling the film mold from the cured resin layer and winding it on the roll It is characterized by including.
- the film mold 3 is wound on the locking layer 2 of the roll 1 whose surface has locking capability. At that time, the film mold 3 is wound on the roll 1 with the surface not having the concavo-convex pattern on the surface side of the roll 1, that is, the surface having the concavo-convex pattern on the outside. Then, the film mold 3 is held on the roll 1.
- the film mold 3 when the length of the roll outer periphery direction of the film mold 3 is shorter than the outer periphery of the roll 1, the entire length of the film mold 3 is wound around the roll 1, and the length of the film mold 3 in the outer peripheral direction of the roll However, when it is longer than the outer periphery of the roll 1, the film mold 3 corresponding to the length of the outer periphery of the roll is wound around the roll 1, and the film mold corresponding to the length longer than the outer periphery of the roll is wound thereon.
- the roll 1 preferably has a diameter of 23 to 1000 mm and a width of 10 to 3000 mm.
- Examples of the material of the roll 1 include metal, carbon, plastic, silicone rubber, and ceramic.
- the roll 1 is connected to normal driving means and rotates.
- the locking ability means a function of holding the film mold 3 so as to be detachable. And from the viewpoint of reliably locking the film mold 3, it is preferable that the entire surface of the roll 1 has a locking capability.
- the locking ability of the surface of the roll 1 include static electricity, reduced pressure, and adhesion, but it is preferable to use adhesion from the viewpoint of handling.
- An example of the above static electricity is to use the relationship of the charged column.
- the polyester is easily negatively charged. For this reason, it is possible to increase the electrostatic force by selecting glass or lead that is easily positively charged as the material of the roll.
- the coulomb force can be generated on the surface of a medium such as polyimide, alumina ceramics, or quartz glass, and the voltage can be applied to the roll to adjust the locking ability of the roll.
- the roll locking ability can be adjusted by providing pores in the roll, suctioning the pressure through the pores, and adjusting the degree of vacuum from 0.1 kPa to 0.1 MPa.
- the adhesive include a method of applying an adhesive on the roll surface and a method of sticking an adhesive sheet on the roll surface.
- a pressure-sensitive adhesive mainly composed of an acrylic resin, a urethane resin, a silicone resin, and rubber can be used.
- An adhesive is preferred.
- These pressure-sensitive adhesives preferably contain a crosslinking agent such as an isocyanate compound or a metal chelate compound as necessary.
- a method of applying the pressure-sensitive adhesive to the roll surface a known method such as painting with a brush or spraying can be used.
- a sticky elastomer sheet is stuck to the roll directly or by using an adhesive, or a double-sided tape having a pressure-sensitive adhesive layer is used.
- a method of sticking to a roll and making the other side a pressure-sensitive adhesive layer having a locking ability is used as a method of sticking the pressure-sensitive adhesive sheet to the roll surface.
- Elastomer sheet materials include natural rubber, silicone rubber, ethylene-propylene copolymer rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber, styrene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, Examples include chlorinated polyethylene, urethane rubber, fluorine rubber, chloroprene rubber, isobutylene isoprene rubber, and polyester.
- double-sided tape in addition to those in which a pressure-sensitive adhesive layer is formed on both sides of the base material, those that do not use a base material (releasability after release treatment laminated on both sides of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer) Any one of those formed only from the base material) can be used, but considering the ease of sticking to the film mold and the ease of work when replacing the film mold, the adhesive is applied to both sides of the base material.
- the double-sided tape formed is preferable, and in particular, it is preferable to use a double-sided tape whose adhesive strength on the side to be attached to the film mold is weaker than the adhesive strength on the surface attached to the roll.
- the base material used for the double-sided tape it is only necessary to have flexibility that can be wound around a roll. Specifically, a thermoplastic resin film, a nonwoven fabric, a foam, or the like can be used.
- the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer constituting the double-sided tape can be a pressure-sensitive adhesive mainly composed of acrylic resin, urethane resin, silicone resin, and rubber, but it is easy to adjust the cost and the adhesive force described later. Therefore, an adhesive mainly composed of an acrylic resin is preferable.
- These pressure-sensitive adhesives preferably contain a crosslinking agent such as an isocyanate compound or a metal chelate compound as necessary.
- the pressure-sensitive adhesive layer preferably has an adhesive strength at 23 ° C. of less than 20 N / 25 mm at a tensile angle of 90 ° and a peeling speed of 300 mm / min in accordance with JIS Z 0237. More preferably, it is 10 N / 25 mm.
- the film mold has a resin layer having a concavo-convex pattern on the surface, preferably a film base, a resin layer formed on the film base and having a concavo-convex pattern on the surface, and at least a concavo-convex pattern of the resin layer. And a release agent layer formed with a uniform thickness on the surface.
- the film substrate is preferably a resin selected from the group consisting of polyethylene terephthalate, polycarbonate, polyester, polymethyl methacrylate, polystyrene, polyolefin, polyimide, polysulfone, polyethersulfone, and polyethylene naphthalate.
- the thickness of the film substrate is preferably in the range of 25 to 1000 ⁇ m in order to achieve both flexibility and rigidity.
- the resin forming the resin layer include a thermoplastic resin, a thermosetting resin, and a photocurable resin.
- acrylic resin, methacrylic resin, styrene resin, olefin resin, cycloolefin resin, polycarbonate resin, polyester resin, epoxy resin, oxetane, and the like can be given.
- Preferred resins are photo-curing resins, especially resins that are cured by ultraviolet rays.
- the resin may contain components such as an antioxidant, a photosensitizer, a filler, and a leveling agent in a range that does not affect the properties of the resin.
- the thickness of the resin layer is usually 0.5 to 500 ⁇ m, preferably 5 to 250 ⁇ m. When the thickness of the resin layer is within the above range, the resin layer has strength to withstand imprinting, has good smoothness, is flexible, and is easy to handle.
- the thickness of the resin layer refers to the distance between the bottom surface of the resin layer and the surface with the highest surface irregularities.
- the concavo-convex pattern on the surface of the resin layer is a pattern repeated at a constant cycle, and preferably has a cycle of 10 nm to 500 ⁇ m and a depth of 10 nm to 500 ⁇ m.
- Specific examples of the uneven shape include an uneven shape including a line, a cylinder, a monolith, a cone, a polygonal pyramid, a microlens, a wiring pattern, a hole-like hole, and the like.
- Examples of the release agent that forms the release agent layer include a fluorine-based silane coupling agent, a perfluoro compound having an amino group or a carboxyl group, and a perfluoroether compound having an amino group or a carboxyl group.
- the thickness of the release agent layer is preferably in the range of 0.5 to 20 nm.
- the uniform thickness means a substantially uniform thickness, preferably a uniform thickness with a standard deviation of 0.1 to 10.
- the inorganic layer is preferably made of at least one inorganic material selected from the group consisting of SiO 2 , ZrO 2 , ZnO, Ta 2 O 5 , HfO 2 , ITO, FTO, TiO 2 , Si and SiC.
- the thickness is preferably in the range of 0.5 to 100 nm.
- the length in the outer peripheral direction of the roll of the film mold is not particularly limited, and may be shorter or longer than the outer periphery of the roll, but may be shorter than the outer periphery of the roll from the viewpoint of stably locking to the roll. preferable.
- the length in the roll width direction of the film mold is preferably shorter than the roll width from the viewpoint of imprinting.
- a substrate 5 and an object to be transferred in which an uncured object resin layer 4a to be transferred is laminated on the substrate 5 are placed and fixed.
- substrate 5 A resin substrate, a glass substrate, a silicon substrate, a sapphire substrate, a gallium nitride substrate, a carbon substrate, a silicon nitride substrate etc. can be mentioned,
- In order to raise adhesiveness with to-be-transferred resin. Can be subjected to known easy adhesion treatment (corona treatment, primer treatment, etc.).
- the substrate 5 can be appropriately selected according to the intended use of the resulting concavo-convex pattern formed body, but a resin substrate is preferable from the viewpoint of flexibility and cost.
- the resin used for the resin substrate include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, cyclic polyolefin, polyimide, polysulfone, polyethersulfone, and polyethylene naphthalate.
- the thickness of the substrate is preferably in the range of 25 to 2000 ⁇ m, and more preferably in the range of 50 to 500 ⁇ m.
- thermoplastic resins examples include thermoplastic resins, thermosetting resins, and photocurable resins.
- Preferred resins include photocurable resins, particularly resins that are cured by ultraviolet rays. Specific examples include acrylic resins, methacrylic resins, cycloolefin resins, styrene resins, epoxy resins, polycarbonate resins, and polyester resins.
- a thermoplastic resin usually requires a pretreatment that is heated and softened before application or dissolved in an organic solvent, whereas a photocurable resin is required. In this case, it is preferable in that no pretreatment is required.
- the thickness of the transferred resin layer 4a can be appropriately selected according to the intended use of the resulting concavo-convex pattern forming body, but is preferably in the range of 0.1 to 100 ⁇ m.
- quartz, glass, stone surface plate, metal, plastic and the like are usually used as the material for the substrate platform 6.
- an indwelling means 7 for temporarily fixing the end of the film mold 3 is provided on the substrate platform 6.
- the indwelling means 7 is preferably provided at an end portion of the substrate 5 on the substrate platform 6, and more preferably provided at both ends of the substrate 5.
- Examples of the indwelling means 7 include a removable adhesive tape, silicone rubber, and a locking piece that is mounted so as to straddle between the film mold and the substrate mounting portion.
- the positional accuracy of the imprint particularly in continuous work is ensured, and the locking of the film mold 3 on the transferred resin layer 4 a is assisted.
- the method for fixing the transferred body on the substrate mounting portion 6 include a vacuum suction method, fixing with a fixing jig, and an adhesive method using an adhesive.
- ⁇ Step (3)> Preferably, after the end of the film mold 3 is fixed by the indwelling means 7, as shown in FIG. 1 (3), a process is performed on the surface of the transferred resin layer 4 a on the substrate 5 prepared in the process (2). While the film mold 3 wound around the roll 1 obtained in (1) is in contact, the roll is rotated in the unwinding direction, and the uneven pattern on the surface of the film mold 3 is formed on the surface of the transferred resin layer 4a. Transcript. Then, since the locking ability of the transferred resin layer 4a with respect to the film mold 3 is greater than the capability of locking the film mold 3 of the roll 1, the film mold 3 peels off from the surface of the roll 1 simultaneously with the transfer of the concavo-convex pattern.
- the film mold 3 moves from the roll 1 onto the transferred material resin layer 4a.
- the film mold 3 can be laminated on the transferred resin layer 4a without generating bubbles.
- the film mold 3 does not have to be completely peeled off from the roll 1, and a part of the film mold 3 may remain wound around the roll 1.
- the pressure of the roll 1 is preferably 1 Pa to 10 kPa, and the rotation speed is preferably 0.001 to 2 m / min.
- Examples of the resin curing means include light irradiation means and heating means.
- Examples of the light used for the light irradiation means include active energy rays such as ultraviolet rays, visible rays, infrared rays, and electron beams. The irradiation amount of the active energy ray is usually 1 to 20,000 mJ / cm 2 .
- Examples of the heating means include an electric heater, an infrared heater (lamp), and induction heating.
- the light irradiation means is used when the transfer body resin is a photocurable resin, and the heating means is used when the transfer body resin is a thermosetting resin.
- the transfer resin is a thermoplastic resin, it is possible to achieve the same purpose as the curing in the present invention by solidifying. Therefore, the solidified thermoplastic resin is used as the transfer resin layer 4b. Can do.
- a roll 1 having a locking ability on the surface is brought into contact with the film mold 3 laminated on the surface of the transferred resin layer 4b cured in the step (4).
- the ability of the transferred resin layer 4b obtained by curing the transferred resin layer 4a to the film mold 3 is reduced, and the cured transferred resin layer 4b is locked to the film mold 3.
- the film mold 3 is peeled off from the cured transfer material resin layer 4 b and wound around the roll 1.
- the peeling angle when the film mold 3 is peeled from the cured transfer resin layer 4b is only the roll curvature, and therefore the film mold 3 and the cured transfer resin layer 4b may be damaged. Absent.
- the pressure of the roll 1 is preferably 1 Pa to 10 kPa, and the rotation speed is preferably 0.001 to 2 m / min from the viewpoint of reliably peeling the film mold 3 from the cured transfer resin layer 4b. .
- the roll used in the step (4) may be a roll with the film mold 3 peeled off in the step (3), or a roll different from the roll used in the steps (1) to (3). May be.
- the present invention is an invention utilizing the fact that the interfacial adhesive strength between the film mold and the transferred resin layer is relatively lowered by the pressure and rotation of the roll 1 and the transferred resin layer being cured.
- the transferred resin layer has wettability because it is fluid before curing.
- the cured transfer resin layer is a cured resin, it has no wettability, and the substrate has high adhesion to the transfer resin layer.
- the adhesiveness (adhesiveness) between the roll and the film mold can be set higher than the peeling force at the interface of the transfer resin layer, and the film mold can be wound around the roll.
- the present invention has a lower locking ability on the surface of the roll 1 than the locking ability between the transferred resin layer 4a and the substrate before curing, and the relationship between the cured film mold and the transferred resin layer 4b. Set higher than stopping power.
- the magnitude relationship between the locking ability of the surface of the roll 1 and the locking ability of the transferred resin layer is reversed by decreasing the adhesion to the film mold 3 due to curing of the transferred resin layer.
- the roll surface and the transferred resin layer are reciprocated.
- step (3) preferably, after the end of the film mold 3 is fixed to the substrate mounting part 6 by the indwelling means 7, the film mold is brought into contact with the untransferred resin layer 4a before curing. Then, since the locking capability of the roll 1 surface is lower than the locking capability of the transferred resin layer 4a before curing, the film mold can be applied from the surface of the roll 1 before curing by pressurizing and developing (rotating) the roll 1. It moves on the transferred resin layer 4a. On the other hand, when the locking layer on the surface of the roll 1 is brought into contact with the cured transfer target resin layer 4b in the step (5), the locking capability of the roll 1 surface is the locking capability of the transferred transfer resin layer before curing. Since it is higher, the film mold moves from the cured resin layer to the roll surface by the pressurization and development (rotation) of the roll 1.
- the present invention can easily peel off the film mold 3 from the roll surface, and can collect the film mold on the roll surface after the concavo-convex pattern formed body is manufactured. Therefore, according to the production method of the present invention, the transfer operation and the curing operation of the transferred resin layer can be performed separately, and the recovered film mold can be reused.
- the roll 1 having the locking ability on the surface and the resin curing means are fixed, and the substrate mounting portion is moved, thereby continuously forming the uneven pattern forming body. Can be manufactured.
- the concavo-convex pattern formed body obtained in the present invention can be used for optical members (antireflection film, wire grid type polarizing plate, LED and OLED light extraction substrate by appropriately adjusting the size of the concavo-convex pattern and the composition of the transferred resin. , A light diffusion plate, etc.), a cell culture sheet, a water repellent member, and a hydrophilic member.
- An imprint apparatus includes a roll having a locking ability on a surface, a film mold having a concavo-convex pattern on the surface that is unwound and held on the roll surface, and a transfer resin
- the transferred resin layer on which the concavo-convex pattern of the film mold is transferred by placing the roll on the transferred resin layer after curing and rotating the roll in the winding direction of the film mold;
- the film mold is peeled off, and the film mold can be wound up and collected on a roll surface.
- Adhesive A 120 g (solid content) of acrylic polymer (manufactured by Soken Chemical Co., Ltd., product name: SK Dyne 1435, non-volatile content 30%), 3 isocyanate crosslinking agent (manufactured by Tosoh Corp., Coronate HX, non-volatile content 100%) .6 g (solid content) and 200 g of ethyl acetate were mixed.
- Adhesive B 120 g (solid content) of acrylic polymer (manufactured by Soken Chemical Co., Ltd., product name: SK Dyne 1495, 30% non-volatile content), 12 g of isocyanate cross-linking agent (manufactured by Tosoh Corp., Coronate HX, 100% non-volatile content) (Solid content) and 200 g of ethyl acetate were mixed.
- a pressure-sensitive adhesive layer A was formed by applying and drying pressure-sensitive adhesive A on one side of a 50 ⁇ m-thick polyethylene terephthalate film (Toray Industries, Lumirror T60). Moreover, the adhesive layer B was formed by applying and drying the adhesive B on the other surface of the polyethylene terephthalate film on which the adhesive layer A was not formed. The thickness of each of the pressure-sensitive adhesive layers A and B after drying is 25 ⁇ m, and the pressure-sensitive adhesive layer A has a higher adhesive strength than the pressure-sensitive adhesive layer B.
- the adhesive strength of the adhesive layer A to the stainless steel plate is (7.1 N / 25 mm).
- the adhesive strength of the adhesive layer B to the stainless steel plate is (0.4 N / 25 mm).
- inorganic layer SiO 2 is vacuum-deposited at room temperature for 1 minute on the resin sheet having a shape on the surface obtained in (1) to form an oxide coating film having a thickness of 10 nm. And it was set as the inorganic substance layer. After vapor deposition, it was visually confirmed that the surface shape of the inorganic layer was free of cracks and defects.
- release agent layer A laminate of the inorganic layer, the photocurable resin layer, and the substrate obtained in (2) is used as a perfluoro fluorine release agent (trade name: OPTOOL DSX, manufactured by Daikin Industries, Ltd.). ) And then left to stand in a wet heat environment of 70 ° C. and 90% RH for 1 hour.
- the film was rinsed with a fluorine-based solvent (trade name: HD-TH 3 manufactured by Harves Co., Ltd.), and allowed to stand in an environment of 23 ° C. and 65% RH for 24 hours to complete the treatment of the release agent layer.
- the thickness of the release agent layer was 3 nm. Although the uneven
- Example 1 A double-sided pressure-sensitive adhesive tape was attached to the surface of a roll made of SUS304 having a diameter of 100 mm and a width of 200 mm via the pressure-sensitive adhesive layer A of the double-sided pressure-sensitive adhesive tape obtained in Preparation Example 1.
- the film mold produced in Adjustment Example 2 was wound and held on the roll surface via the pressure-sensitive adhesive layer B of the double-sided pressure-sensitive adhesive tape to obtain a roll having the film mold wound and held on the surface.
- a 100 ⁇ m thick polyethylene terephthalate substrate manufactured by Toray Industries Inc., Lumirror U10 was placed on the substrate placing portion by a tape fixing method.
- a photocurable resin (manufactured by Toyo Gosei Co., Ltd., PAK-02) was applied onto the substrate by a bar coating method to form a transferred resin layer having a thickness of 1.5 ⁇ m.
- the roll on which the film mold is wound and held is brought into contact with the resin layer to be transferred at a pressure of 250 Pa and rotated at a rotational speed of 0.06 m / min in the unwinding direction. Is peeled off at the interface between the film mold and the pressure-sensitive adhesive layer B of the pressure-sensitive adhesive tape and unwound on the surface of the transferred resin layer to transfer the pattern of the film mold to the transferred resin layer and between the transferred resin layer and the film mold.
- a laminate was obtained.
- the laminate of the transferred resin layer and the film mold was irradiated with 1,000 mJ / cm 2 of ultraviolet light to cure the transferred resin.
- the film mold is cured resin. It peeled from the layer and wound up on the adhesive layer B on the roll surface. Neither the film mold nor the transferred resin layer pattern was destroyed.
- Example 1 The transfer resin was not cured when the same operation as in Example 1 was performed except that the amount of ultraviolet irradiation applied to the laminate of the transfer resin layer and the film mold was changed to 40 mJ / cm 2 . When the film mold was rotated in the winding direction of the roll, it was found that the resin layer pattern was deformed and destroyed.
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Abstract
Description
[1]表面が係止能を有するロール上に、表面に凹凸パターンを有するフィルムモールドを着脱可能に巻回保持する工程(1)と、
基板載置部上に基板および基板上に形成された被転写体樹脂層を含む被転写体を載置する工程(2)と、
前記被転写体樹脂層の表面に、前記工程(1)で得られたロールに巻回保持されたフィルムモールドを当接しながらロールを回動させて、フィルムモールドをロール上から剥離して被転写体樹脂層上に巻き出すとともにフィルムモールドの表面の凹凸パターンを被転写体樹脂層に転写する工程(3)と、
前記工程(3)により表面にフィルムモールドが積層された状態の被転写体樹脂層を硬化させる工程(4)と、
前記工程(4)で得られた硬化した被転写体樹脂層上に積層されたフィルムモールドに、表面が係止能を有するロールを当接しながら回動させて、フィルムモールドを硬化した被転写体樹脂層上から剥離してロール上に巻き取る工程(5)とを含むことを特徴とする凹凸パターン形成体の製造方法。
前記フィルムモールドを巻回したロールを前記被転写体樹脂層上に配置して、前記フィルムモールドの巻き出し方向に前記ロールを回動することにより、前記フィルムモールドをロール表面から被転写体樹脂層表面へ供給可能にされており、
かつ、前記樹脂硬化手段により被転写樹脂層の硬化させた後に、
前記ロールを硬化後の前記被転写体樹脂層上に配置して、前記フィルムモールドの巻取り方向にロールを回動することにより、前記フィルムモールドの凹凸パターンが転写された被転写体樹脂層と前記フィルムモールドとを剥離して、前記フィルムモールドをロール表面に巻き取り回収可能にされてなることを特徴とするインプリント装置。
また、本発明のインプリント装置は、従来のロールトゥプレート方式の装置のようにスタンパを支柱や回動アームに取り付ける必要がないので、従来のロールトゥプレート方式の装置に比べて小型化が可能である。
図1(1)に示すように、フィルムモールド3を、表面が係止能を有するロール1の係止層2上に巻回する。その際、フィルムモールド3は、凹凸パターンを有しない面をロール1の表面側にして、すなわち凹凸パターンを有する面を外側にしてロール1上に巻回する。するとフィルムモールド3はロール1上に保持される。なお、フィルムモールド3のロール外周方向の長さが、ロール1の外周よりも短い場合は、フィルムモールド3の全尺をロール1に巻回することになり、フィルムモールド3のロール外周方向の長さが、ロール1の外周よりも長い場合は、ロール外周長さ分のフィルムモールド3をロール1に巻回し、その上に重ねてロール外周より長い分のフィルムモールドを巻回する。
ロール1の大きさは、直径が23~1000mm、幅が10~3000mmであることが好ましい。ロール1の材質としては、金属、カーボン、プラスチック、シリコーンゴム、セラミック等が挙げられる。ロール1は、通常駆動手段に接続され、回動する。
そして、フィルムモールド3を確実に係止する観点から、ロール1表面全体が係止能を有することが好ましい。
ロール1表面の係止能としては、静電気、減圧および粘着等が挙げられるが、取り扱いの観点から粘着を用いることが好ましい。
上記粘着の例としては、ロール表面に粘着剤を塗布する方法、ロール表面に粘着シートを貼付する方法が挙げられる。
フィルムモールドは、表面に凹凸パターンを有する樹脂層を有する、好ましくはフィルム基材と、前記フィルム基材上に形成され、表面に凹凸パターンを有する樹脂層と、前記樹脂層の少なくとも凹凸パターンを有する面上に均一な厚さで形成された剥離剤層とを有する。
樹脂層の厚さは、通常0.5~500μm、好ましくは5~250μmであることが好ましい。樹脂層の厚さが上記範囲にあると、インプリントに耐える強度を有するとともに、平滑性が良く、フレキシブル性があり取扱いが容易である。ここで、樹脂層の厚さとは、樹脂層の底面と表面の凹凸の最も高い面との間の距離をいう。
無機物層は、SiO2、ZrO2、ZnO、Ta2O5、HfO2、ITO、FTO、TiO2、SiおよびSiCよりなる群から選ばれる少なくとも1種の無機物からなることが好ましく、無機物層の厚さは0.5~100nmの範囲内が好ましい。
フィルムモールドのロール幅方向の長さは、インプリントする観点から、ロール幅よりも短いことが好ましい。
図1(2)に示すように、インプリント装置の基板載置部6上に基板5および基板5上に未硬化の被転写体樹脂層4aが積層された被転写体を載置し、固定する。
基板5としては、特に制限されないが、樹脂基板、ガラス基板、シリコン基板、サファイア基板、窒化ガリウム基板、炭素基板、窒化ケイ素基板などを挙げることができ、被転写体樹脂との密着性を上げるために公知の易接着処理(コロナ処理、プライマー処理など)を施すことができる。
基板載置部6の材質としては、通常石英、ガラス、石定盤、金属およびプラスチック等が用いられる。
被転写体を基板載置部6上に固定する方法としては、例えば真空吸着法、固定治具による固定、粘着剤を用いた粘着法等を挙げることができる。
好ましくはフィルムモールド3の端部を留置手段7で固定した後、図1(3)に示すように、工程(2)で準備された基板5上の被転写体樹脂層4aの表面に、工程(1)で得られたロール1に巻回されたフィルムモールド3を当接しながら、前記ロールを巻き出し方向に回動させ、フィルムモールド3の表面の凹凸パターンを被転写体樹脂層4a表面に転写する。すると、フィルムモールド3に対する被転写体樹脂層4aの係止能が、ロール1のフィルムモールド3を係止する能力よりも大きいため、凹凸パターンの転写と同時にフィルムモールド3はロール1表面から剥離し、被転写体樹脂層4a上に巻き出される。その結果、フィルムモールド3は、ロール1から被転写体樹脂層4a上に移動する。この方法によれば、気泡を生じることなく、フィルムモールド3を被転写体樹脂層4a上に積層することができる。なお、フィルムモールド3はロール1から全て剥離する必要はなく、一部はロール1に巻きつけられた状態のままでもよい。
この際、転写を良好にする観点から、ロール1の圧力としては、1Pa~10kPaが好ましく、回転速度としては、0.001~2m/分が好ましい。
図1(4)に示すように、フィルムモールド3は工程(3)で被転写体樹脂層4a上に巻き出されることにより、被転写体樹脂層4a上に積層された状態となる。この状態で、樹脂硬化手段(図示せず)を用いて被転写体樹脂層4aを硬化させて、硬化した被転写体樹脂層4bとする。
図1(5)に示すように、工程(4)で硬化した被転写体樹脂層4b表面上に積層されたフィルムモールド3に、表面が係止能を有するロール1を当接して巻き取り方向に回動させる。すると、被転写体樹脂層4aが硬化することによって得られた被転写体樹脂層4bのフィルムモールド3に対する係止能が減少して、フィルムモールド3に対する硬化した被転写体樹脂層4bの係止能が、ロール1のフィルムモールド3を係止する能力よりも小さくなるために、フィルムモールド3は、硬化した被転写体樹脂層4bから剥離し、ロール1に巻き取られる。この方法では、フィルムモールド3を硬化した被転写体樹脂層4bから剥離する際の剥離角がロール曲率のみとなるため、フィルムモールド3および硬化した被転写体樹脂層の4bに損傷を生じることがない。
本発明は、ロール1の圧力および回転、ならびに被転写体樹脂層が硬化することにより、相対的にフィルムモールドと被転写樹脂層の界面接着強度が低くなる事を利用した発明である。
上記工程(2)における基板載置部が固定されている場合、前記表面にフィルムモールド3を有するロール1を移動させ、被転写体樹脂層4を硬化させることで、連続的に凹凸パターン形成体を製造することができる。この場合ロール1としては、被転写体樹脂層4a上にフィルムモールド3を巻き出すロールと、硬化した被転写体樹脂層4b上からフィルムモールド3を巻き取るロールとで、異なるロールを用いることにより、移動に替えてもよい。
本発明で得られる凹凸パターン形成体は、凹凸パターンの寸法や被転写体樹脂の組成を適宜調整することによって、光学部材用途(反射防止フィルム、ワイヤグリッド型偏光板、LEDやOLEDの光取出し基板、光拡散板など)、細胞培養シート、撥水性部材、親水性部材として好適に用いることができる。
本発明の第二の態様にかかるインプリント装置は、表面に係止能を有するロールと、前記ロール表面に巻出し着脱可能に保持された表面に凹凸パターンを有するフィルムモールドと、被転写体樹脂層を硬化させるための樹脂硬化手段とを備えてなり、前記フィルムモールドの表面に形成された凹凸パターンを被転写体樹脂層に転写するインプリント装置であって、
前記フィルムモールドを巻回したロールを前記被転写体樹脂層上に配置して、前記フィルムモールドの巻き出し方向に前記ロールを回動することにより、前記フィルムモールドをロール表面から被転写体樹脂層表面へ供給可能にされてなり、
かつ、前記樹脂硬化手段により被転写樹脂層の硬化後に、
前記ロールを硬化後の前記被転写体樹脂層上に配置して、前記フィルムモールドの巻取り方向にロールを回動することにより、前記フィルムモールドの凹凸パターンが転写された被転写体樹脂層と前記フィルムモールドとを剥離して、前記フィルムモールドをロール表面に巻き取り回収可能にされてなることを特徴とする。
[調製例1:両面粘着テープの調製]
粘着剤A:アクリル系ポリマー(綜研化学社製、品名:SKダイン1435、不揮発分30%)を120g(固形分量)、イソシアネート系架橋剤(東ソー社製、コロネートHX、不揮発分100%)を3.6g(固形分量)、酢酸エチル200gを混合させた。
粘着剤B:アクリル系ポリマー(綜研化学社製、品名:SKダイン1495、不揮発分30%)を120g(固形分量)、イソシアネート系架橋剤(東ソー社製、コロネートHX、不揮発分100%)を12g(固形分量)、酢酸エチル200gを混合させた。
粘着剤層Aのステンレス板に対する粘着力は(7.1N/25mm)である。
粘着剤層Bのステンレス板に対する粘着力は(0.4N/25mm)である。
(1)樹脂層の形成
イソボルニルアクリレート75重量部、ジペンタエリスリトールヘキサアクリレート15重量部、グリシジルメタクリレート10重量部を混合した光硬化性樹脂液を厚さ75μmのポリエチレンテレフタレートフィルム(東洋紡社製、コスモシャインA-4100)の易接着処理面上に膜厚が1μmになるようにスピンコートしたのち、表面にホール状の凹凸が付与されたニッケルモールド(転写面100mm×100mm・周期250nm・深さ200nm)に0.4MPaで押し付け、UV照射(10mW/cm2、1分)により樹脂膜を硬化させた後、モールドを離型してホール状の穴が付与された樹脂シートを得た。
(1)で得られた表面に形状が付与された樹脂シート上に、SiO2 を室温下、1分間の真空蒸着を行い、10nm厚さの酸化被覆膜を形成し、無機物層とした。蒸着後、無機物層の表面形状にクラックや形状の欠損がないことを目視にて確認した。
(3)剥離剤層の形成
(2)で得られた無機物層と光硬化性樹脂層と基板との積層物を、パーフルオロ系のフッ素系剥離剤(ダイキン工業社製、商品名:オプツールDSX)に1分間浸漬した後、引き上げ70℃ 90%RHの湿熱環境に1時間静置した。その後、フッ素系溶剤(ハーベス社製、商品名:HD-TH )でリンスし、23℃、65%RHの環境で24時間静置し、剥離剤層の処理を完了した。剥離剤層の厚さは3nmであった。剥離剤層の形成後の凹凸形状を確認したが、欠陥や形状変化が無かった。
このようにして、基板、樹脂層、無機物層および剥離剤層がこの順に積層されたフィルムモールドが得られた。
径100mm幅200mmのSUS304製ロールの表面に、調製例1で得られた両面粘着テープの粘着剤層Aを介して両面粘着テープを貼付した。
調整例2で作製したフィルムモールドを前記両面粘着テープの粘着剤層Bを介してロール表面に巻回保持させ、フィルムモールドが表面に巻回保持されたロールを得た。
基板載置部に、厚さ100μmのポリエチレンテレフタレート製基板(東レ社製、ルミラーU10)を、テープ固定法により載置した。
前記フィルムモールドが表面に巻回保持されたロールを、前記被転写樹脂層に、250Paの圧力で当接し、巻き出し方向に0.06m/分の回転速度で回転させ、前記フィルムモールドの全尺をフィルムモールドと前記粘着テープの粘着剤層Bとの界面で剥離して被転写樹脂層表面に巻き出し、フィルムモールドのパターンを被転写樹脂層に転写するとともに被転写樹脂層とフィルムモールドとの積層物を得た。
次に、フィルムモールドが剥離されたロールを、前記積層物のフィルムモールドに250Paの圧力で当接して、巻き取り方向に0.06m/分の回転速度で回転させると、フィルムモールドは硬化した樹脂層から剥離してロール表面の粘着剤層B上に巻き取られた。フィルムモールドや転写された樹脂層のパターンはともに破壊されていなかった。
被転写樹脂層とフィルムモールドとの積層物に対する紫外線の照射量を40mJ/cm2に変更したこと以外は実施例1と同様の操作で行ったところ、被転写樹脂は硬化しなかった。フィルムモールドをロールの巻取り方向に回転させると、樹脂層のパターンが変形・破壊されたものが散見された。
1:ロール
2:係止能を有するロール表面
3:フィルムモールド
4a:硬化前の被転写体樹脂層
4b:硬化後の被転写体樹脂層
5:基板
6:基板載置部
7:留置手段
8:フィルムモールド固定層
Claims (4)
- 表面が係止能を有するロール上に、表面に凹凸パターンを有するフィルムモールドを着脱可能に巻回保持する工程(1)と、
基板載置部上に基板および基板上に形成された被転写体樹脂層を含む被転写体を載置する工程(2)と、
前記被転写体樹脂層の表面に、前記工程(1)で得られたロールに巻回保持されたフィルムモールドを当接しながらロールを回動させて、フィルムモールドをロール上から剥離して被転写体樹脂層上に巻き出すとともにフィルムモールドの表面の凹凸パターンを被転写体樹脂層に転写する工程(3)と、
前記工程(3)により表面にフィルムモールドが積層された状態の被転写体樹脂層を硬化させる工程(4)と、
前記工程(4)で得られた硬化した被転写体樹脂層上に積層されたフィルムモールドに、表面が係止能を有するロールを当接しながら回動させて、フィルムモールドを硬化した被転写体樹脂層上から剥離してロール上に巻き取る工程(5)とを含むことを特徴とする凹凸パターン形成体の製造方法。 - 前記ロール表面に粘着層が存在することを特徴とする請求項1に記載の凹凸パターン形成体の製造方法。
- 前記工程(1)~(5)を連続して行うこと特徴とする請求項1または2に記載の凹凸パターン形成体の製造方法。
- 表面に係止能を有するロールと、前記ロール表面に巻出し着脱可能に保持された表面に凹凸パターンを有するフィルムモールドと、被転写樹脂層を硬化させるための樹脂硬化手段とを備えてなり、前記フィルムモールドの表面に形成された凹凸パターンを被転写体樹脂層に転写するインプリント装置であって、
前記フィルムモールドを巻回したロールを前記被転写体樹脂層上に配置して、前記フィルムモールドの巻き出し方向に前記ロールを回動することにより、前記フィルムモールドをロール表面から被転写体樹脂層表面へ供給可能にされており、
かつ、前記樹脂硬化手段により被転写樹脂層の硬化させた後に、
前記ロールを硬化後の前記被転写体樹脂層上に配置して、前記フィルムモールドの巻取り方向にロールを回動することにより、前記フィルムモールドの凹凸パターンが転写された被転写体樹脂層と前記フィルムモールドとを剥離して、前記フィルムモールドをロール表面に巻き取り回収可能にされてなることを特徴とするインプリント装置。
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KR102384120B1 (ko) * | 2019-06-26 | 2022-04-07 | 한국기계연구원 | 실시간 정렬이 가능한 미세패턴 롤 제작시스템, 및 이를 이용한 미세패턴 롤 제작방법 |
CN113534605A (zh) * | 2021-06-30 | 2021-10-22 | 昆山华冠商标印刷有限公司 | 一种纹路压印模板的制备方法 |
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- 2016-03-15 WO PCT/JP2016/058060 patent/WO2016148118A1/ja active Application Filing
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TW201641294A (zh) | 2016-12-01 |
CN107405824A (zh) | 2017-11-28 |
JPWO2016148118A1 (ja) | 2017-12-28 |
KR20170126862A (ko) | 2017-11-20 |
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