JP2012056085A - Method of manufacturing cylindrical mold and apparatus for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a cylindrical mold advantageously usable in nano imprint, with high productivity and precision.SOLUTION: The method of manufacturing a cylindrical mold having a fine irregular pattern on the outer peripheral surface comprises, while rotating a cylindrical transfer plate 50 having an outer cylindrical part 20 consisting of a light-transmissive cylindrical member 12 and a light-curable transfer layer 13 formed on the outer peripheral surface of the cylindrical member 12 and being deformable by pressurization, bringing the transfer layer 13 of the outer cylindrical part 20 into pressed contact with the fine irregular pattern 72 of an original mold 70 moving in the same direction as that of the cylindrical transfer plate 50 and having a fine irregular pattern so as to transfer the fine irregular pattern 72 to the transfer layer 13 and irradiating transfer areas 15 of the transfer layer 13 with UV rays from the side of the inner periphery of the outer cylindrical part 20, at the same time as the transferring, to harden the transfer layer 13 in order to form a reversed irregular pattern continuously in the transfer layer 13.

Description

  The present invention relates to a nanoimprint cylindrical mold that can be advantageously used in the manufacture of electronic devices, optical components, recording media, and the like, and more particularly to a method for manufacturing a large-diameter cylindrical mold and an apparatus used for the method.

  Progress in microfabrication technology using light or electron beam is remarkable, and processing is achieved with accuracy of 100 nm for light and 10 nm for electron beam. However, since these fine processing apparatuses are expensive, a cheaper processing technique is required. In accordance with such a purpose, a method of forming a desired circuit pattern or the like on a silicon substrate or the like by nanoimprint technology is being established. The nanoimprint technology is a microfabrication technology for realizing a finer structure as compared with the conventional press technology. This technique itself has no limit in resolution, and the resolution is determined by the accuracy of mold (ie, mold) production. Therefore, as long as the mold can be manufactured, it is possible to form an ultrafine structure with an apparatus that is easier and much cheaper than conventional photolithography.

  In general, nanoimprint uses a flat mold in which a concavo-convex pattern is formed on the surface of a substrate such as silicon, quartz, nickel or the like, and the concavo-convex pattern is transferred to a thermoplastic resin or a photocurable resin. On the other hand, in order to improve productivity, a method of performing nanoimprinting in a short time using a cylindrical (roller type) mold has been proposed (for example, Patent Document 1).

  When producing a mold for nanoimprinting, for example, the following is performed. A silicon substrate has a silicon dioxide surface formed by thermal oxidation, and a positive electron beam resist (for example, polymethyl methacrylate (PMMA)) is coated on the surface. The resist is exposed to a fine pattern with an electron beam, and thereafter development, chromium deposition, lift-off (step of removing chromium on the resist and leaving only chromium on the substrate), dry etching (other than the portion masked with chromium) The step of removing the silicon dioxide layer) is performed, and finally the chromium is removed to complete the mold (see Non-Patent Document 1). Patent Document 1 discloses a cylindrical mold manufactured by a method in which a mold manufactured on such a silicon substrate is provided on a cylindrical portion.

  Thus, the production of a flat plate or cylindrical mold requires a great deal of labor and time. In addition, although exposure with an electron beam has a resolution capable of producing a fine pattern of 10 nm or less, there is a problem that it takes a very long time for drawing because of one stroke writing, and productivity cannot be increased.

  For the nanoimprint mold, a large area is preferable in terms of productivity improvement, but it is extremely difficult to directly produce a large area mold (a large diameter mold in the case of a cylindrical shape) by the method described above. It is.

  In Patent Document 2, in order to make a roll stamper (that is, a cylindrical mold) a large area, a master roll is manufactured by pressing and engraving from a flat master, and a circle having an area larger than that of the master roll. A method is disclosed in which a roll stamper is scaled up by repeating a process of pressing and engraving a transfer roll having a peripheral portion several times.

JP 2008-073902 A JP 2004-042475 A

“First nanoimprint technology” Jun Taniguchi, p. 35-36 (2005) Industrial Research Co., Ltd.

  However, since the method of Patent Document 2 uses indentation engraving, it is considered difficult to transfer a fine uneven pattern with high accuracy.

  Accordingly, an object of the present invention is to provide a method for manufacturing a cylindrical mold that can be advantageously used for nanoimprinting, in particular, a large-diameter cylindrical mold, which can be manufactured with high productivity and high accuracy. is there.

  Moreover, this invention is providing the apparatus which uses the cylindrical mold for manufacture.

  The above object is a method for producing a cylindrical mold having a fine uneven pattern on its outer peripheral surface, from a light-transmitting cylindrical member and a photocurable transfer layer deformable by pressure formed on its outer peripheral surface. While rotating the cylindrical transfer plate having the outer cylindrical portion, the fine layer of the original mold having a fine concavo-convex pattern on the surface that moves the transfer layer of the outer cylindrical portion in the same direction as the cylindrical transfer plate. Touching the concavo-convex pattern under pressure, transferring the fine concavo-convex pattern to the transfer layer, and simultaneously irradiating the transfer region of the transfer layer with ultraviolet rays from the inner peripheral side of the outer circumferential portion and curing This is achieved by a method for producing a cylindrical mold, wherein a reverse concavo-convex pattern is continuously formed on the transfer layer.

  In the present invention, the photocurable transfer layer is a layer that can be accurately transferred by pressing the surface of the fine concavo-convex pattern of the mold.

  When trying to transfer the concavo-convex pattern from the original mold to a cylindrical member with a photocurable transfer layer formed on the outer peripheral surface, if a normal opaque roll substrate is used, the photocurable transfer is performed with the original mold pressed. The layer cannot be irradiated with UV light. Therefore, after the original mold is pressed, it is moved slightly, and the portion where the transfer layer is exposed is irradiated with ultraviolet rays and cured. With this method, it is not possible to form the concave / convex pattern on the cylindrical member with high accuracy.

  In the present invention, by using a cylindrical transfer plate in which a photocurable transfer layer is formed on the outer peripheral surface of a light transmissive cylindrical member, it is possible to irradiate the photocurable transfer layer with ultraviolet rays from the inner peripheral side of the cylindrical member. I have to. Then, while rotating the cylindrical transfer plate, the concave / convex pattern of the original mold is transferred to the photocurable transfer layer by bringing the photocurable transfer layer into contact with the original mold under pressure, and the cylindrical member is transferred to the transfer region. By irradiating ultraviolet rays from the inner peripheral side of the substrate and curing the transfer region, a reverse concavo-convex pattern can be continuously formed on the transfer layer.

The suitable aspect of the manufacturing method of the cylindrical mold of this invention is as follows.
(1) Ultraviolet light that allows the cylindrical transfer plate to locally irradiate a part of the transfer layer with ultraviolet light on the inner peripheral side of the outer cylindrical part and to move the ultraviolet light irradiating area. An irradiation unit is provided. Thereby, irradiation of the ultraviolet rays from the inner peripheral side of the cylindrical member in the present invention can be easily performed.
(2) The inner cylindrical portion made of an ultraviolet shielding cylindrical member, the ultraviolet irradiation portion being rotatable independently of the outer cylindrical portion, and having a slit in part.
An ultraviolet lamp provided inside the inner cylindrical portion,
A condensing unit that collects ultraviolet rays irradiated from the slit to the outer peripheral side; and a shutter provided in the slit and capable of controlling on / off of the irradiation of the ultraviolet rays and an irradiation range. Thereby, the local ultraviolet irradiation in the present invention can be performed with higher accuracy.
(3) The condensing part is a cylindrical lens. Thereby, it can condense on the area | region on a line | wire and can condense an ultraviolet-ray with higher precision.
(4) The light-transmitting cylindrical member has a transmittance in the thickness direction of a wavelength of 300 to 450 nm of 80% or more and a haze in the thickness direction of 3.0 or less. Thereby, hardening of a photocurable transfer layer can be performed at higher speed, and production efficiency can be improved.
(5) The said photocurable transfer layer consists of a photocurable composition containing the reactive diluent which has a polymer and a photopolymerizable functional group. Thereby, it can be set as the photocurable transfer layer hardened | cured more rapidly.
(6) The original mold is a cylindrical original mold. Thereby, a cylindrical mold can be manufactured more efficiently.
(7) The diameter of the cylindrical transfer plate is larger than the diameter of the cylindrical original mold. Thereby, since it can transfer continuously to a large-diameter cylindrical transfer plate using a small-diameter cylindrical original mold, a large-diameter cylindrical mold can be manufactured efficiently.

Further, the object is to provide a light-transmitting cylindrical member, an outer cylindrical portion made of a photocurable transfer layer deformable by pressure formed on the outer peripheral surface thereof, and an inner peripheral side of the outer cylindrical portion, A cylindrical transfer plate provided with an ultraviolet irradiation unit capable of locally irradiating ultraviolet rays to a partial region of the transfer layer and moving the ultraviolet irradiation region;
An original mold having a fine concavo-convex pattern on the surface, disposed opposite to the cylindrical transfer plate,
While rotating the cylindrical transfer plate, the transfer layer of the outer cylindrical portion is brought into contact with the original mold under pressure, and a press rotating means for transferring a fine uneven pattern of the original mold to the transfer layer, and Ultraviolet irradiation that locally irradiates the transfer region of the transfer layer with ultraviolet rays from the ultraviolet irradiation unit and moves the ultraviolet irradiation region in conjunction with the movement of the transfer region as the cylindrical transfer plate rotates. It is also achieved by a cylindrical mold manufacturing apparatus comprising a control means. By the said apparatus, the manufacturing method of the cylindrical mold of this invention can be implemented suitably.

The suitable aspect of the manufacturing apparatus of the cylindrical mold of this invention is as follows.
(1) The inner cylindrical portion made of an ultraviolet shielding cylindrical member, the ultraviolet irradiation portion being rotatable independently of the outer cylindrical portion, and having a slit in a part thereof,
An ultraviolet lamp provided inside the inner cylindrical portion,
A condensing unit that collects ultraviolet rays irradiated from the slit to the outer peripheral side; and a shutter provided in the slit and capable of controlling on / off of the irradiation of the ultraviolet rays and an irradiation range. Thereby, it can be set as the apparatus which performs the local ultraviolet irradiation in this invention with high precision.
(2) The condensing part is a cylindrical lens. Thereby, it can focus on the area | region on a line | wire and it can be set as the apparatus which condenses an ultraviolet-ray with higher precision.
(3) The light-transmitting cylindrical member has a transmittance in the thickness direction of a wavelength of 300 to 450 nm of 80% or more and a haze in the thickness direction of 3.0 or less. Thereby, it can be set as the apparatus which can harden | cure a photocurable transfer layer at higher speed.
(4) The said photocurable transfer layer consists of a photocurable composition containing the reactive diluent which has a polymer and a photopolymerizable functional group. Thereby, it can be set as the photocurable transfer layer hardened | cured more rapidly.
(5) The said original mold is a cylindrical original mold. Thereby, it can be set as the apparatus which can manufacture a cylindrical mold more efficiently.
(6) The diameter of the cylindrical transfer plate is larger than the diameter of the cylindrical original mold. Thereby, since it can be continuously transferred to a large-diameter cylindrical transfer plate using a small-diameter cylindrical original mold, an apparatus capable of efficiently producing a large-diameter cylindrical mold can be provided.

  In the method for producing a cylindrical mold according to the present invention, since a cylindrical transfer plate having a photocurable transfer layer formed on the outer peripheral surface of a light transmissive cylindrical member is used, photocuring is performed from the inner peripheral side of the cylindrical member. The transfer layer can be irradiated with ultraviolet rays. Then, while rotating the cylindrical transfer plate, the concave / convex pattern of the original mold is transferred to the photocurable transfer layer by bringing the photocurable transfer layer into contact with the original mold under pressure, and the cylindrical member is transferred to the transfer region. By irradiating ultraviolet rays from the inner peripheral side of the substrate and curing the transfer region, a reverse concavo-convex pattern can be continuously formed on the transfer layer.

  Therefore, according to the method of the present invention, it is possible to provide a cylindrical mold having a high-precision transfer of the concave / convex pattern of the original mold with high productivity.

It is a schematic sectional drawing which shows an example of embodiment of the cylindrical transfer plate used for this invention. In the manufacturing method of the cylindrical mold of this invention, it is a schematic sectional drawing which shows an example using the flat plate-shaped original mold. In the manufacturing method of the cylindrical mold of this invention, it is a schematic sectional drawing which shows an example using the cylindrical original mold.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a cylindrical transfer plate used in the method for producing a cylindrical mold of the present invention. The cylindrical transfer plate 50 has an outer cylindrical portion 20 composed of a light-transmissive glass or plastic cylindrical member 12 and a photocurable transfer layer 13 that is deformed by pressure formed on the outer peripheral surface thereof. The ultraviolet irradiation unit 30 is provided on the inner peripheral side. The ultraviolet irradiation unit 30 includes a mechanism capable of locally irradiating ultraviolet rays from the inner peripheral side to a part of the photocurable transfer layer 11 of the outer cylindrical portion 20 and moving the ultraviolet irradiation region. It is preferable.

  The ultraviolet irradiation unit 30 in FIG. 1 is rotatable independently of the outer cylindrical part 20, and includes an inner cylindrical part 22 made of an ultraviolet shielding metal or plastic cylindrical member having a slit 24 in part, and an inner cylindrical part 22. Are provided with an ultraviolet lamp 23 provided inside, a condensing part 25 for condensing ultraviolet rays irradiated from the slit 24 to the outer peripheral side in a predetermined region, and slits 24 are provided to turn on / off ultraviolet irradiation and to irradiate ultraviolet rays. A shutter 26 capable of controlling the range is provided. With such an ultraviolet irradiation unit 30, it is possible to easily irradiate a partial area of the photocurable transfer layer 13 locally from the inner peripheral side of the outer cylindrical unit 20, and the cylindrical transfer plate 50. This is preferable because the ultraviolet irradiation region can be moved in conjunction with the rotation of. The condensing part 25 may be anything as long as it can locally condense on a predetermined region of the photocurable transfer layer 13, but a cylindrical lens that can condense on the region on the line is preferable. The shutter 26 is preferably a shutter that can control not only the circumferential width of the slit 24 of the inner cylindrical portion 22 but also the axial width so that the ultraviolet irradiation range can be further limited.

  The outer cylindrical part 20 and the ultraviolet irradiation part 30 may be integrated, but a cartridge type in which the outer cylindrical part 20 can be detached from the ultraviolet irradiation part 30 and another outer cylindrical part can be mounted is preferable in terms of cost.

  As long as the cylindrical member 12 in the outer cylindrical part 20 is light transmissive so that it can be cured by irradiating the photocurable transfer layer 13 formed on the outer peripheral surface with ultraviolet rays from the inner peripheral side, Things can be used. Preferably, the transmittance of the cylindrical member 12 at a wavelength of 300 to 450 nm in the thickness direction is 80% or more, and the haze in the thickness direction is 3.0 or less. Thereby, it can be set as the apparatus which can harden | cure a photocurable transfer layer at higher speed. Examples of the material of the cylindrical member 12 include glass or ultraviolet transparent transparent plastics such as polyethylene and polypropylene. The thickness of the cylindrical member 12 is not particularly limited as long as it has a strength that does not cause breakage when transferred from the original mold or when used as a cylindrical mold. In general, the thickness is 0.5 to 10.0 mm, preferably 1.0 to 5.0 mm.

  The photocurable transfer layer 13 in the outer cylindrical portion 20 can be deformed by pressurization, and by pressing the fine uneven pattern surface of the original mold, the inverted uneven pattern can be accurately transferred and peelable after curing. It is also an excellent transfer layer. In the present invention, the photocurable composition forming the photocurable transfer layer 11 is preferably a polymer, a photopolymerizable functional group (generally a carbon-carbon double bond group, preferably a (meth) acryloyl group (acryloyl group). And a reactive diluent (monomer and oligomer) having a methacryloyl group, the same shall apply hereinafter)), and optionally further comprising a photopolymerizable initiator and other additives. Details of these will be described later.

[Manufacturing method of cylindrical mold]
The manufacturing method of the cylindrical mold of this invention is demonstrated in detail, referring drawings.
The method for producing a cylindrical mold of the present invention uses a cylindrical transfer plate 50 as described above, and an original mold having a fine concavo-convex pattern on the surface that moves in the same direction as the cylindrical transfer plate 50 while rotating it. The concavo-convex pattern is brought into contact under pressure, and the concavo-convex pattern is transferred to the photocurable transfer layer 13. At the same time, the transfer region of the photocurable transfer layer 13 is irradiated with ultraviolet rays from the inner peripheral side of the outer circumferential portion. In this method, a reverse concavo-convex pattern is continuously formed on the transfer layer by curing. The original mold can be a flat original mold or a cylindrical original mold.

  FIG. 2 is a schematic cross-sectional view showing an example of using a flat plate mold in the method for producing a cylindrical mold of the present invention.

  First, a part of the photocurable transfer layer 13 on the outer peripheral surface of the cylindrical transfer plate 50 rotating in the direction of the arrow is brought into contact with a part of the fine concavo-convex pattern 62 of the flat plate precursor mold 60 under pressure. Since the cylindrical transfer plate 50 is cylindrical, a linear transfer region 15 having a certain width is formed in the photocurable transfer layer 13 at a contact portion with the flat plate mold 60. Then, ultraviolet rays are locally applied to the transfer region 15 from the ultraviolet irradiation unit 30, and the transfer region 15 in the photocurable transfer layer 13 is locally cured (FIG. 2A).

  At this time, it is possible to accurately irradiate only the transfer region 15 with ultraviolet rays by controlling the inner cylindrical portion 22 having the slit 24 as described above and the ultraviolet irradiation unit 30 having the shutter 26.

  Since the cylindrical transfer plate 50 is rotated in the direction of the arrow and the flat plate mold 60 is moved in the direction of the arrow (the same direction as the cylindrical transfer plate 50), from the cured transfer region 15c of the photocurable transfer layer 13. A part of the concavo-convex pattern 62 of the flat plate mold 60 is peeled off to form the reverse concavo-convex pattern 17 on the transfer region 15 c, and another part of the photocurable transfer layer 13 is formed of the concavo-convex pattern of the flat plate original mold 60. Another part of the pattern 62 is brought into contact under pressure, and another transfer region 15 ′ is formed in the photocurable transfer layer 13 (FIG. 2B).

  At this time, the ultraviolet irradiation unit 30 moves the ultraviolet irradiation region in conjunction with the movement of the transfer region of the photocurable transfer layer 13 to the transfer region 15 ′ with the rotation of the cylindrical transfer plate 50. By controlling to, the steps shown in FIGS. 2A and 2B can be performed continuously. Thereby, the reverse uneven | corrugated pattern 17 can be formed in the whole region of the photocurable transfer layer 13. FIG. The ultraviolet irradiation control means for setting the range of the ultraviolet irradiation region and controlling the movement of the irradiation region may be incorporated in the cylindrical transfer plate 50 or may be controlled by an external signal.

  The size of the flat plate precursor mold 60 is not particularly limited. When the length of the plate-shaped original mold 60 is less than the circumference of the cylindrical transfer plate 50, the rotation of the cylindrical transfer plate 50 is stopped at the end of the plate-shaped original mold 60, and the plate-shaped original mold 60 is shifted and transfer is resumed. By repeating this operation, the inverted concavo-convex pattern 17 can be formed in the entire area of the photocurable transfer layer 13. Further, when the width of the flat plate mold 60 is less than the axial length of the cylindrical transfer plate 50, the cylindrical transfer plate 50 is rotated once in a state of being pressed against the flat plate mold 60; The inverted concavo-convex pattern 17 can be formed in the entire region of the photocurable transfer layer 13 by repeating the same operation while shifting the flat plate mold 60 by the width. At this time, it is necessary not to cure the photocurable transfer layer 13 other than the transfer region by narrowing the width in the axial direction of the ultraviolet irradiation region by the ultraviolet irradiation unit 30 to the width of the flat plate mold 60.

  FIG. 3 is a schematic cross-sectional view showing an example using a cylindrical original mold in the method for producing a cylindrical mold of the present invention. Except that the original mold is rotated together with the cylindrical transfer plate 50, it is the same as the case of using the above-mentioned flat original mold.

  First, a part of the photocurable transfer layer 13 on the outer peripheral surface of the cylindrical transfer plate 50 rotating in the direction of the arrow is brought into contact with a part of the fine uneven pattern 72 of the cylindrical original mold 70 under pressure. Since the cylindrical transfer plate 50 is cylindrical, a linear transfer region 15 having a certain width is formed in the photocurable transfer layer 13 at a contact portion with the cylindrical original mold 70. Then, ultraviolet rays are locally irradiated from the ultraviolet irradiation unit 30 to the transfer region 15, and the transfer region 15 in the photocurable transfer layer 13 is locally cured (FIG. 3A).

  At this time, it is possible to accurately irradiate only the transfer region 15 with ultraviolet rays by controlling the inner cylindrical portion 22 having the slit 24 as described above and the ultraviolet irradiation unit 30 having the shutter 26.

  Since the cylindrical transfer plate 50 is rotated in the direction of the arrow and the cylindrical original mold 70 is rotated in the direction of the arrow (the same direction as the cylindrical transfer plate 50), from the cured transfer region 15c of the photocurable transfer layer 13. A part of the concavo-convex pattern 72 of the cylindrical original mold 70 is peeled off to form the reverse concavo-convex pattern 17 on the transfer region 15 c, and another part of the photocurable transfer layer 13 is an uneven part of the cylindrical original mold 70. Another part of the pattern 72 is brought into contact under pressure, and another transfer region 15 ′ is formed in the photocurable transfer layer 13 (FIG. 2B).

  At this time, the ultraviolet irradiation unit 30 moves the ultraviolet irradiation region in conjunction with the movement of the transfer region of the photocurable transfer layer 13 to the transfer region 15 ′ with the rotation of the cylindrical transfer plate 50. By controlling to, the steps shown in FIGS. 2A and 2B can be performed continuously. Thereby, the reverse uneven | corrugated pattern 17 can be formed in the whole region of the photocurable transfer layer 13. FIG. The ultraviolet irradiation control means for setting the range of the ultraviolet irradiation region and controlling the movement of the irradiation region may be incorporated in the cylindrical transfer plate 50 or may be controlled by an external signal.

  In the case of the cylindrical original mold 70, since there is no end in the length direction unlike the flat original mold, the photocurable transfer layer 13 of the cylindrical transfer plate 50 is continuously formed at any diameter. It is preferable because the concave / convex pattern can be transferred to the entire area. Further, in this case, the diameter of the cylindrical transfer plate 50 is preferably larger than the diameter of the cylindrical original plate mold 70. As described above, since the original mold is manufactured in a very complicated process, a small-diameter mold can be manufactured and scaled up to a large-diameter cylindrical mold by the method of the present invention.

  The axial width of the cylindrical original mold 70 is not particularly limited. When the axial length of the cylindrical master plate 70 and the axial length of the cylindrical transfer plate 50 are not satisfied, the cylindrical transfer plate 50 is rotated once while being pressed against the cylindrical master mold 70. The concave / convex pattern 17 can be formed in the entire area of the photocurable transfer layer 13 by repeating the same operation while shifting the cylindrical original mold 70 by the axial width thereof. At this time, it is necessary not to cure the photocurable transfer layer 13 other than the transfer region by narrowing the axial width of the ultraviolet irradiation region by the ultraviolet irradiation unit 30 to the axial width of the cylindrical original mold 70. It is.

In the present invention, the irradiation amount of the ultraviolet ray to the transfer region is not particularly limited, but is preferably 300 mJ / cm ² or more. Alternatively, partial curing may be performed without completely curing in this step, and the inverted concavo-convex pattern may be transferred to the entire area of the photocurable transfer layer 13, and then UV irradiation may be sufficiently performed again to complete curing.

  The flat plate mold 60 and the cylindrical flat plate mold 70 may be any mold (mold). A mold used for the nanoimprint process method or the like is preferable because it is advantageous for transferring a fine uneven pattern. Any material may be used, but preferably nickel, titanium, silicon, quartz or the like can be applied.

  Below, the preferable aspect of the photocurable transfer layer 13 in the cylindrical transfer plate 50 used for the method of this invention is described.

[Photocurable transfer layer]
As described above, in the present invention, the photocurable composition forming the photocurable transfer layer 13 is preferably a polymer, a photopolymerizable functional group (generally a carbon-carbon double bond group, preferably (meth) acryloyl). A reactive diluent (monomer and oligomer) having a group (which represents an acryloyl group and a methacryloyl group; the same shall apply hereinafter), and further comprises a photopolymerizable initiator and other additives as desired.

[polymer]
Examples of the polymer constituting the photocurable composition include acrylic resin, polyvinyl acetate, vinyl acetate / (meth) acrylate copolymer, ethylene / vinyl acetate copolymer, polystyrene and its copolymer, polyvinyl chloride and its Copolymer, butadiene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3-polymer, chlorinated rubber, styrene / butadiene / Examples thereof include styrene copolymers, styrene / isoprene / styrene block copolymers, epoxy resins, polyamides, polyesters, polyurethanes, cellulose esters, cellulose ethers, polycarbonates, and polyvinyl acetals.

  The polymer in the present invention is preferably an acrylic resin from the viewpoint of good transferability and excellent curability. As described above, the acrylic resin is particularly preferably an acrylic resin having a polymerizable functional group or an acrylic resin having a hydroxyl group. In addition, when the acrylic resin contains at least 50% by mass (especially 60 to 90% by mass) of methyl methacrylate repeating units, it is easy to obtain an acrylic resin having a Tg of 80 ° C. or more, and good transferability and high-speed curability are also obtained. It is easy and preferable.

  Moreover, it is preferable that the polymer which comprises a photocurable composition is a polymer whose glass transition temperature (Tg) is 80 degreeC or more. Thereby, the fine uneven | corrugated pattern of a metal mold | die can be transcribe | transferred easily, and hardening can also be performed at high speed. Further, since the cured shape also has a high Tg, the shape can be maintained for a long time without changing. A polymer having a glass transition temperature of 80 ° C. or higher has a polymerizable functional group, which can react with a reactive diluent and is advantageous in increasing the speed of curing. In addition, by including a diisocyanate in the transfer layer 11 by having a hydroxyl group, it is possible to slightly crosslink the polymer, and in particular, a layer in which the transfer layer oozes out and the layer thickness fluctuation is greatly suppressed can be obtained. It is advantageous. Diisocyanates are effective to some extent even in polymers without hydroxyl groups.

In the present invention, when an acrylic resin is used as the polymer, an acrylic resin having a polymerizable functional group or an acrylic resin having a hydroxyl group is particularly preferable.
In the present invention, the acrylic resin having a polymerizable functional group is a copolymer having glycidyl (meth) acrylate as a monomer component, and the glycidyl group reacts with a carboxylic acid having a polymerizable functional group, or is polymerizable. It is a copolymer having a carboxylic acid having a functional group as a monomer component, and glycidyl (meth) acrylate is reacted with the carboxylic acid group.

  The glycidyl (meth) acrylate or carboxylic acid having a polymerizable functional group is preferably contained in the polymer in an amount of generally 5 to 25% by mass, particularly 5 to 20% by mass as the repeating unit. The glycidyl group or carboxylic acid group of the obtained copolymer is reacted with a carboxylic acid or glycidyl (meth) acrylate having a polymerizable functional group, respectively.

  In addition, as a monomer component, methyl (meth) acrylate, alcohol residue (meth) acrylic acid ester having 2 to 10 carbon atoms, alicyclic group having 3 to 12 carbon atoms (alicyclic ring) (Meth) acrylic acid ester having a formula hydrocarbon group and an alicyclic ether group) may be included. Alkyl (meth) acrylic acid ester having 2 to 10 carbon atoms (especially 3 to 5 carbon atoms) as an alcohol residue includes ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. Examples of the acrylate ester having an alicyclic group include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. As other monomer components, methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable. Such a (meth) acrylic acid ester is preferably contained in the polymer as a repeating unit in general in an amount of 5 to 30% by mass, particularly 10 to 30% by mass.

  The acrylic resin having the polymerizable functional group can be produced, for example, as follows.

  One or a plurality of (meth) acrylate monomers and a compound having 1 glycidyl group and 1 polymerizable functional group (preferably glycidyl (meth) acrylate) or a carboxylic acid having a polymerizable functional group are radicals. A glycidyl group-containing acrylic resin (a) or a carboxyl group-containing acrylic resin (b) as a copolymer is obtained by reacting with a known method such as a solution polymerization method in the presence of a polymerization initiator and an organic solvent.

  Subsequently, a carboxylic acid having a polymerizable functional group is added to the obtained glycidyl group-containing acrylic resin (a), or one glycidyl group and one polymerizable functional group are added to the obtained carboxyl group-containing acrylic resin (b). An acrylic photocurable resin (A) or an acrylic photocurable resin (B) is obtained by adding a compound (preferably glycidyl methacrylate) having heat and heating as necessary. This blending ratio is preferably blended so that the molar ratio of glycidyl group to carboxyl group is 1 / 0.9 to 1/1, and more preferably 1/1. If the glycidyl group is excessive, viscosity and gelation may occur in long-term stability, and if the carboxyl group is excessive, skin irritation increases and workability decreases. Further, in the case of 1/1, there is no residual glycidyl group, and the storage stability is remarkably improved. The reaction can be carried out by a known method in the presence of a basic catalyst, a phosphorus catalyst or the like.

  In the present invention, the acrylic resin having a hydroxyl group generally includes methyl methacrylate, at least one kind of (meth) acrylic acid ester having 2 to 10 carbon atoms and an alcohol residue having a hydroxyl group. It is a copolymer with at least one kind of alkyl (meth) acrylic acid ester having 2 to 4 carbon atoms. Methyl methacrylate is preferably contained as a repeating unit in an amount of 50% by mass or more (particularly 60 to 90% by mass) in the polymer. Appropriate combination with the reactive diluent makes it easy to achieve both good transferability and excellent curability.

  Alkyl (meth) acrylic acid ester having 2 to 10 carbon atoms (especially 3 to 5 carbon atoms) as an alcohol residue includes ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferred. Further, such a (meth) acrylic acid ester is preferably contained in the polymer as a repeating unit in general in an amount of 5 to 30% by mass, particularly 10 to 30% by mass.

  Examples of the alkyl (meth) acrylic acid ester having 2 to 4 carbon atoms in which the alcohol residue has a hydroxyl group include 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate. In general, it is preferably contained in an amount of 5 to 25% by mass, particularly 5 to 20% by mass.

  In addition, as a monomer component, you may contain the (meth) acrylic acid ester which has a C3-C12 alicyclic group (an alicyclic hydrocarbon group and an alicyclic ether group are included) besides. . Examples of the acrylate ester having an alicyclic group include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  In the present invention, the polymer preferably has a number average molecular weight of 90000 or more, particularly 90000 to 1000000, and a weight average molecular weight of 90000 or more, particularly 90000 to 300000.

  In the present invention, a polymer having both a functional group having an active hydrogen such as a hydroxyl group and a photopolymerizable functional group can also be used as the polymer (preferably having a glass transition temperature of 80 ° C. or higher). As such a reactive polymer, for example, a homopolymer or a copolymer (that is, an acrylic resin) mainly obtained from the acrylic monomer, and a photopolymerizable functional group and active hydrogen are present in the main chain or side chain. It has a functional group. Therefore, such a reactive polymer includes, for example, methyl methacrylate, the one or more (meth) acrylates, and a (meth) acrylate having a functional group such as a hydroxyl group (eg, 2-hydroxyethyl (meth) acrylate). ) And the resulting polymer reacts with a functional group of the polymer and a compound having a photopolymerizable group, such as isocyanatoalkyl (meth) acrylate. In that case, the polymer which has a hydroxyl group and a photopolymerizable functional group as a functional group which has active hydrogen is obtained by adjusting and using the amount of isocyanatoalkyl (meth) acrylate so that a hydroxyl group may remain.

  Alternatively, in the above, a photopolymerizable functional group having an amino group as a functional group having active hydrogen by using a (meth) acrylate having an amino group instead of a hydroxyl group (eg, 2-aminoethyl (meth) acrylate) A containing polymer can be obtained. Similarly, a photopolymerizable functional group-containing polymer having a carboxyl group or the like as a functional group having active hydrogen can also be obtained.

  In the present invention, an acrylic resin having the photopolymerizable functional group via a urethane bond is also preferable.

  The polymer having a photopolymerizable functional group generally contains 1 to 50 mol%, particularly 5 to 30 mol% of the photopolymerizable functional group. As this photopolymerizable functional group, an acryloyl group, a methacryloyl group, and a vinyl group are preferable, and an acryloyl group and a methacryloyl group are particularly preferable.

[Reactive diluent]
In this invention, the following are mentioned as a reactive diluent (monomer and oligomer) which has a photopolymerizable functional group contained in a photocurable transfer composition. For example, (meth) acrylate monomers include 1,6-hexanediol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, benzyl (meth) acrylate, phenyloxyethyl (meth) acrylate, tetrahydrofurfuryl ( (Meth) acrylate, acryloylmorpholine, N-vinylcaprolactam, o-phenylphenyloxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neope Cyl glycol di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycerin diacrylate, glycerin acrylate methacrylate, glycerin dimethacrylate , Trimethylolpropane diacrylate, trimethylolpropane acrylate methacrylate, trimethylolpropane dimethacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acrylic Roxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate , Mention may be made of dimethylol tricyclodecane (meth) acrylate, isobornyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, and the like. (Meth) acrylate oligomers include polyol compounds (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol). , 2-ethyl-2-butyl-1,3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxydiol, polytetramethylene glycol and other polyols A polyol which is a reaction product of the polyol and a polybasic acid such as succinic acid, maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid, terephthalic acid, or an acid anhydride thereof. Terpolyols, polycaprolactone polyols which are a reaction product of the polyols and ε-caprolactone, a reaction product of the polyols and the ε-caprolactone of a polybasic acid or an acid anhydride thereof, a polycarbonate polyol, Polymer polyols) and organic polyisocyanates (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethyl) Hexamethylene diisocyanate, 2,2 ′, 4-trimethylhexamethylene diisocyanate and the like) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2 Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, cyclohexane-1,4-dimethylol mono (meth) acrylate, pentaerythritol tri (meth) A reaction product of polyurethane (meth) acrylate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc., which is a reaction product of acrylate, glycerin di (meth) acrylate, etc., and bisphenol, which is a reaction product of (meth) acrylic acid Type epoxy (meth) acrylate and the like. These compounds having a photopolymerizable functional group can be used alone or in combination of two or more.

  In the present invention, the mass ratio of the polymer of the photocurable composition to the reactive diluent is preferably in the range of 20:80 to 80:20, particularly 30:70 to 70:30.

[Photopolymerization initiator]
As the photopolymerization initiator contained in the photocurable composition forming the photocurable transfer layer, any known photopolymerization initiator can be used, but it has good storage stability after blending. Is desirable. Examples of such photopolymerization initiators include benzoin series such as acetophenone series and benzyldimethyl ketal, thiophenone series such as benzophenone series, isopropylthioxanthone, and 2-4-diethylthioxanthone, and other special types include methylphenylglycol. Oxylate can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may contain one or two or more kinds of known and commonly used photopolymerization accelerators such as benzoic acid-based or tertiary amine-based compounds such as 4-dimethylaminobenzoic acid as required. Can be mixed and used. Moreover, it can be used by 1 type, or 2 or more types of mixture of only a photoinitiator. In general, the photocurable composition (nonvolatile content) preferably contains 0.1 to 20% by mass, particularly 1 to 10% by mass of a photopolymerization initiator.

  Among the photopolymerization initiators, examples of the acetophenone-based polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-2. -Methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2 As benzophenone polymerization initiators such as morpholinopropane-1, Benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, 4-Benzzoiru 4'-methyl diphenyl sulfide, etc. 3,3'-dimethyl-4-methoxybenzophenone may be used.

  As the acetophenone-based polymerization initiator, in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2 -Morpholinopropane-1 is preferred. As the benzophenone polymerization initiator, benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate are preferable. Tertiary amine photopolymerization accelerators include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate. , Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and the like can be used. Particularly preferably, as the photopolymerization accelerator, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, etc. Is mentioned.

[Diisocyanate]
In the present invention, when diisocyanate is added as a curing agent to the photocurable composition forming the photocurable transfer layer, tolylene diisocyanate (TDI), isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4-diisocyanate. Dicyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate, 2,2 ′, 4-trimethylhexamethylene diisocyanate can be used. Polyisocyanate cyanates such as trifunctional or higher functional isocyanate compounds such as a TDI adduct of trimethylolpropane can also be used. Of these, a hexamethylene diisocyanate adduct of trimethylolpropane is preferred.

  In the present invention, the diisocyanate is preferably contained in the photocurable composition (nonvolatile content) in the range of 0.2 to 4% by mass, particularly 0.2 to 2% by mass. Appropriate crosslinking is provided to prevent the transfer layer from seeping out, and good transferability of the unevenness of a mold such as a stamper is also maintained. The reaction between the compound and the polymer proceeds gradually after the transfer layer is formed, and reacts considerably at room temperature (generally 25 ° C.) at 24 hours. It is considered that the reaction proceeds after the coating solution for forming the transfer layer is prepared and before the coating solution is applied. After forming the transfer layer, it is preferable to cure to a certain extent before winding it in the roll state. If necessary, the reaction is promoted by heating during the formation of the transfer layer or before winding in the roll state. You may let them.

[Others]
In the present invention, it is preferable to add the following thermoplastic resin and other additives to the photocurable composition for forming the photocurable transfer layer, if desired.

  As another additive, a lubricant (release agent) can be added in order to further improve the releasability. Examples of the lubricant include phosphoric acid-containing polyalkylene compounds, phosphoric acid trialkyl ester compounds, phosphorus atom-containing compounds such as phosphates and phosphoric acid amides, and silicone resins such as non-modified or modified polysiloxanes. The addition amount of the lubricant is usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymer (solid content).

  Moreover, a silane coupling agent (adhesion promoter) can be added as another additive. As this silane coupling agent, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β There are (aminoethyl) -γ-aminopropyltrimethoxysilane and the like, and one of these can be used alone or two or more of them can be used in combination. As for the addition amount of these silane coupling agents, 0.01-5 mass parts is sufficient normally with respect to 100 mass parts of said polymers (solid content).

  Similarly, an epoxy group-containing compound can be added for the purpose of improving adhesiveness. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate; neopentyl glycol diglycidyl ether; 1,6-hexanediol diglycidyl ether; acrylic glycidyl ether; 2-ethylhexyl glycidyl ether; Examples thereof include phenol glycidyl ether; pt-butylphenyl glycidyl ether; adipic acid diglycidyl ester; o-phthalic acid diglycidyl ester; glycidyl methacrylate; Further, the same effect can be obtained by adding an oligomer containing an epoxy group having a molecular weight of several hundred to several thousand or a polymer having a weight average molecular weight of several thousand to several hundred thousand. The addition amount of these epoxy group-containing compounds is sufficient to be 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer (solid content), and at least one of the epoxy group-containing compounds is added alone or in combination. Can do.

  Furthermore, as another additive, a hydrocarbon resin can be added for the purpose of improving workability such as workability and bonding. In this case, the added hydrocarbon resin may be either a natural resin type or a synthetic resin type. In natural resin systems, rosin, rosin derivatives, and terpene resins are preferably used. For rosin, gum-based resins, tall oil-based resins, and wood-based resins can be used. As the rosin derivative, rosin obtained by hydrogenation, heterogeneity, polymerization, esterification, or metal chloride can be used. As the terpene resin, a terpene phenol resin can be used in addition to a terpene resin such as α-pinene and β-pinene. In addition, dammar, corbal and shellac may be used as other natural resins. On the other hand, in the synthetic resin system, petroleum resin, phenol resin, and xylene resin are preferably used. As the petroleum resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, pure monomer petroleum resin, and coumarone indene resin can be used. As the phenol resin, an alkyl phenol resin or a modified phenol resin can be used. As the xylene-based resin, a xylene resin or a modified xylene resin can be used.

  Although the addition amount of resin, such as the said hydrocarbon resin, is selected suitably, 1-20 mass parts is preferable with respect to 100 mass parts of said polymers (solid content), More preferably, it is 5-15 mass parts.

  In addition to the above additives, the photocurable composition of the present invention may contain a small amount of an ultraviolet absorber, an antioxidant, a dye, a processing aid and the like. In some cases, additives such as fine particles such as silica gel and calcium carbonate may be contained in a small amount.

In the present invention, the storage elastic modulus at a frequency of 1 Hz of the photocurable transfer layer is preferably 1 × 10 ⁷ Pa or less at 25 ° C., and particularly in the range of 1 × 10 ^{4 to} 6 × 10 ⁵ Pa. preferable. Moreover, it is preferable that it is 8 * 10 < ⁴ > Pa or less in 80 degreeC, and it is especially preferable that it is the range of 1 * 10 < ⁴ > -5 * 10 < ⁵ > Pa. This enables accurate and quick transfer. Furthermore, the photocurable transfer layer of the present invention preferably has a glass transition temperature of 20 ° C. or lower. Thereby, when the obtained photocurable transfer layer is pressure-bonded to the uneven surface of a mold such as a stamper, it can have flexibility to closely follow the uneven surface even at room temperature. In particular, when the glass transition temperature is in the range of 15 ° C. to −50 ° C., and further in the range of 0 ° C. to −40 ° C., the followability is high. If the glass transition temperature is too high, a high pressure and a high pressure are required at the time of bonding, leading to a decrease in workability. If it is too low, sufficient hardness after curing cannot be obtained.

Moreover, in this invention, it is preferable that the photocurable transfer layer is designed so that the glass transition temperature after 300mJ / cm < ² > ultraviolet irradiation may be 65 degreeC or more. By irradiating with ultraviolet rays for a short time, it is easy to prevent the occurrence of sagging such as a pit shape that is likely to occur due to residual stress during transfer, and the transferred pit shape can be retained.

  In order to form the photocurable transfer layer 13 on the outer peripheral surface of the cylindrical member 12, any method may be used. The constituents of the above-mentioned photocuring composition are uniformly mixed, kneaded with an extruder, roll, etc., then formed into a film by a film forming method such as calendering, roll, T-die extrusion, inflation, etc. and wound around the cylindrical member 12 The method or each constituent component is uniformly mixed and dissolved in a good solvent, and applied to the cylindrical member 12 by a flow coating method, a roll coating method, a gravure roll method, a Myer bar method, a lip die coating method, etc., and the solvent is dried. Examples include a method for forming a film.

  In addition, a photocurable transfer sheet in which a photocurable transfer layer 13 is formed on a transparent film made of a polymer film having an easy-adhesion layer on the surface is wrapped around and bonded to the cylindrical member 12 on the transparent film side to be bonded. 13 may be formed. At this time, in terms of handling properties, a release sheet may be provided on the photocurable transfer layer 13, and the release sheet may be removed and used at the time of use.

  Further, using a photocurable transfer sheet having release sheets on both sides of the photocurable transfer layer 13, the photocurable transfer layer 13 is wound around and adhered to the cylindrical member 12 while peeling one of the release sheets. In use, the other release sheet may be removed and used.

  A method of attaching the photocurable transfer layer 13 to the cylindrical member 12 by using a photocurable transfer sheet having a release sheet on both sides capable of forming the photocurable transfer layer 13 with a stable layer thickness is preferable.

  The thickness of the photocurable transfer layer 13 is preferably 1 to 300 μm, particularly preferably 3 to 100 μm.

[Cylindrical mold manufacturing equipment]
The cylindrical mold manufacturing apparatus of the present invention is a manufacturing apparatus that can be advantageously used in the above-described cylindrical mold manufacturing method. For example, as shown in FIG. 3A, an outer cylindrical portion 20 composed of a light-transmissive cylindrical member 12 and a photocurable transfer layer 13 that is deformable by pressure formed on the outer peripheral surface thereof, and an outer side A cylindrical transfer plate 50 having an ultraviolet irradiation unit 30 capable of locally irradiating a part of the photocurable transfer layer 13 on the inner peripheral side of the cylindrical part 20 and moving the irradiation area, a cylindrical shape It is composed of an original mold 70 having a fine uneven pattern on the surface facing the transfer plate 50.

Then, the cylindrical mold manufacturing apparatus of the present invention brings the photocurable transfer layer 13 of the outer cylindrical portion 20 into contact with the original mold 70 under pressure while rotating the cylindrical transfer plate 50, so that the fineness of the original mold 70 can be reduced. Pressing and rotating means for transferring the uneven pattern 72 to the photocurable transfer layer 13;
The transfer region 15 of the photocurable transfer layer 13 is locally irradiated with ultraviolet rays from the ultraviolet irradiation unit 30, and in conjunction with the movement of the transfer region 15 as the cylindrical transfer plate 50 rotates, the ultraviolet irradiation region is changed. An ultraviolet irradiation control means for moving is provided.

  For the ultraviolet irradiation control means, the ultraviolet irradiation section 30 can rotate independently of the outer cylindrical section 20, and the inner cylindrical section 22 made of an ultraviolet shielding metal or plastic cylindrical member having a slit 24 in part. An ultraviolet lamp 23 provided inside the inner cylindrical portion 22, a condensing portion 25 for condensing the ultraviolet rays irradiated from the slit 24 to the outer peripheral side in a predetermined area, and a slit 24 are provided. It is preferable to provide a shutter 26 that can control the cutting range and the irradiation range of ultraviolet rays. The condensing part 25 may be anything as long as it can locally condense on a predetermined region of the photocurable transfer layer 13, but a cylindrical lens that can condense on the region on the line is preferable. The shutter 26 is preferably a shutter that can control not only the circumferential width of the slit 24 of the inner cylindrical portion 22 but also the axial width so that the ultraviolet irradiation range can be further limited.

  The outer cylindrical part 20 and the ultraviolet irradiation part 30 may be integrated, but a cartridge type in which the outer cylindrical part 20 can be detached from the ultraviolet irradiation part 30 and another outer cylindrical part can be mounted is preferable in terms of cost.

  The rotation pressing means and the ultraviolet irradiation control means described above can be performed by incorporating a known drive device or control mechanism into the device of the present invention.

  In addition, this invention is not limited to said embodiment, A various deformation | transformation is possible within the range of the summary of invention. For example, a cylindrical mold having a larger diameter or a plurality of intermediate cylindrical molds may be manufactured by performing the cylindrical mold manufacturing method of the present invention a plurality of times.

  By the cylindrical mold manufacturing method of the present invention, electronic display ribs, electronic devices (lithography, transistors), optical components (microlens arrays, waveguides, optical filters, photonic crystals), bio-related materials (DNA chips, microreactors) In addition, a cylindrical mold advantageous for manufacturing a recording medium (patterned media, DVD) or the like can be obtained with high accuracy and at low cost.

12 Cylindrical member 13 Photo-curable transfer layer 15, 15 'Transfer region 15c Transfer region (after curing)
17 Inverted concavo-convex pattern 20 Outer cylindrical portion 22 Inner cylindrical portion 23 UV lamp 24 Slit 25 Condensing portion 26 Shutter 30 Ultraviolet irradiation portion 50 Cylindrical transfer plate 60 Flat plate mold 62, 72 Concavity and convexity pattern 70 Cylindrical plate mold

Claims (12)

A method for producing a cylindrical mold having a fine uneven pattern on the outer peripheral surface,
While rotating a cylindrical transfer plate having an outer cylindrical portion composed of a light transmissive cylindrical member and a photocurable transfer layer that can be deformed by pressurization formed on its outer peripheral surface,
The transfer layer of the outer cylindrical portion is brought into contact with the fine concavo-convex pattern of the original mold having a fine concavo-convex pattern on the surface moving in the same direction as the cylindrical transfer plate, and the fine concavo-convex pattern is formed. Transferred to the transfer layer,
Simultaneously with the transfer, a reverse concavo-convex pattern is continuously formed in the transfer layer by irradiating the transfer region of the transfer layer with ultraviolet rays from the inner peripheral side of the outer circumferential portion and curing it. A method for producing a cylindrical mold.   The cylindrical transfer plate has, on the inner peripheral side of the outer cylindrical portion, an ultraviolet irradiation unit that can locally irradiate a part of the transfer layer with ultraviolet rays and move the ultraviolet irradiation region. The manufacturing method of Claim 1 provided. The ultraviolet irradiation part is rotatable independently of the outer cylindrical part, and an inner cylindrical part made of an ultraviolet shielding cylindrical member having a slit in part,
An ultraviolet lamp provided inside the inner cylindrical portion,
A condensing unit that collects ultraviolet rays irradiated from the slit to the outer peripheral side; and a shutter provided in the slit, capable of controlling on / off of the irradiation of the ultraviolet rays, and an irradiation range;
The manufacturing method of Claim 2 containing this.   The manufacturing method according to claim 3, wherein the light collecting unit is a cylindrical lens.   5. The light-transmitting cylindrical member has a transmittance in the thickness direction of a wavelength of 300 to 450 nm of 80% or more and a haze in the thickness direction of 3.0 or less. 5. The manufacturing method as described.   The method according to any one of claims 1 to 5, wherein the photocurable transfer layer comprises a photocurable composition comprising a reactive diluent having a polymer and a photopolymerizable functional group.   The manufacturing method according to claim 1, wherein the original mold is a cylindrical original mold.   The manufacturing method according to claim 7, wherein a diameter of the cylindrical transfer plate is larger than a diameter of the cylindrical original plate mold. A light-transmitting cylindrical member and an outer cylindrical portion made of a photocurable transfer layer deformable by pressurization formed on the outer peripheral surface thereof, and a part of the transfer layer on the inner peripheral side of the outer cylindrical portion A cylindrical transfer plate comprising an ultraviolet irradiation unit capable of locally irradiating the region with ultraviolet rays and movable in the region irradiated with the ultraviolet rays;
An original mold having a fine concavo-convex pattern on the surface, disposed opposite to the cylindrical transfer plate,
While rotating the cylindrical transfer plate, the transfer layer of the outer cylindrical portion is brought into contact with the original mold under pressure, and a press rotating means for transferring a fine uneven pattern of the original mold to the transfer layer, and Ultraviolet irradiation that locally irradiates the transfer region of the transfer layer with ultraviolet rays from the ultraviolet irradiation unit and moves the ultraviolet irradiation region in conjunction with the movement of the transfer region as the cylindrical transfer plate rotates. An apparatus for producing a cylindrical mold, comprising: a control unit. The ultraviolet irradiation part is rotatable independently of the outer cylindrical part, and an inner cylindrical part made of an ultraviolet shielding cylindrical member having a slit in part,
An ultraviolet lamp provided inside the inner cylindrical portion,
A condensing unit that collects ultraviolet rays irradiated from the slit to the outer peripheral side; and a shutter provided in the slit, capable of controlling on / off of the irradiation of the ultraviolet rays, and an irradiation range;
The manufacturing apparatus of Claim 9 containing.   The manufacturing apparatus according to claim 10, wherein the light collecting unit is a cylindrical lens.   The light-transmitting cylindrical member has a transmittance at a wavelength of 300 to 450 nm in the thickness direction of 80% or more and a haze in the thickness direction of 3.0 or less. The manufacturing apparatus as described.

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