JP2013229532A - Microstructure transfer device and microstructure transfer method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a microstructure transfer device having excellent transfer accuracy in which releasing properties can be ensured even if continuous transfer is repeated, and to provide a microstructure transfer method.SOLUTION: Releasing properties are ensured and transfer failure is prevented by coating the surface of a resin having fluidity before transfer with a mold release agent, and always forming a constant amount of mold-release layer on the boundary surface of the resin and a mold. Adhesion of the mold release agent to the mold surface is suppressed by using a perfluoro compound or a siloxane compound having, at the terminal thereof, a curable fluid and a parent fluid part including a functional group having reactivity, as the mold-release agent being applied onto the resin surface.

Description

  The present invention relates to a microstructure transfer apparatus for forming a fine uneven pattern on a surface of a transfer object by pressing a mold having a fine uneven pattern on the surface of the transfer object, and a method for forming the same.

  2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. However, the processing method has approached the wavelength of the light source for light exposure, and the lithography technology has also approached its limit. Therefore, in order to advance further miniaturization and higher accuracy, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in place of lithography technology.

  Unlike the batch exposure method in pattern formation using a light source such as i-line or excimer laser, pattern formation using an electron beam takes a method of drawing a mask pattern. The exposure (drawing) takes time and the pattern formation takes time. For this reason, as the degree of integration is dramatically increased to 256 mega, 1 giga, and 4 giga, the pattern formation time is remarkably increased correspondingly, and there is a concern that the throughput is extremely inferior. Therefore, in order to increase the speed of the electron beam drawing apparatus, development of a collective figure irradiation method in which various shapes of masks are combined and irradiated with an electron beam collectively to form an electron beam with a complicated shape is underway. . As a result, while miniaturization of the pattern is promoted, the electron beam lithography apparatus must be enlarged and a mechanism for controlling the mask position with higher accuracy is required. was there.

  On the other hand, a nanoimprint technique is known as a technique for forming a fine pattern at a low cost. The nanoimprint technology is a technology in which a mold having a fine concavo-convex pattern on the order of nanometers is embossed on a resin applied to the surface of a substrate, and a shape in which the concavo-convex pattern of the mold is inverted is transferred.

  As nanoimprint transfer methods, thermal nanoimprint using a thermoplastic resin and optical nanoimprint using a photocurable resin are known. Thermal nanoimprint is a method in which a mold is pressed in a state where a thermoplastic resin is heated and softened to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer a fine pattern of the mold. On the other hand, the optical nanoimprint is to transfer a fine pattern of a mold by curing the photocurable resin by irradiating light with the mold pressed against the photocurable resin and releasing the mold.

  As a nanoimprint pressurization method, a method using a parallel plate type pressurization mechanism in which a mold and a transfer target are placed in parallel and pressurized, and a transfer target is pressed while rotating a roll-shaped mold. A method using a roller type pressure mechanism is known.

In a mold used for such a nano-implement technique, a mold release layer is formed on the mold surface in order to improve the mold release from the transfer target. However, as the transfer is repeated, the release layer on the surface of the mold deteriorates, causing a transfer failure due to a decrease in release properties, and clogging of the mold may occur. For such problems, it is possible to improve the releasability by re-molding the mold, but it is necessary to remove the mold release agent or resin that has deteriorated on the mold surface before the mold release treatment. Therefore, it is not suitable for mass production.
On the other hand, as a technique for improving mold releasability from a transfer target, Patent Document 1 discloses that a substrate and a mold covered with a plurality of coating layers including an imprint resist layer are pressure-bonded to each other. A nanoimprint lithography method in which a structured nanoscale pattern is provided on the substrate by transferring a reverse pattern from the mold to the substrate, the top layer having a pure anti-adhesion function before pressing Disclosed is a method comprising the step of providing a covering layer on the top surface of the substrate.

JP 2005-159358 A

  According to the technique of Patent Document 1, since the coating layer having the anti-adhesion function is formed on the surface of the imprint resist layer to which the pattern is transferred, it is possible to solve the problem of mold release failure due to deterioration of the mold side release layer. . However, in the method of providing a release layer on the surface of the imprint resist layer, when the transfer is continuously repeated, the release layer on the surface of the imprint resist layer adheres to the mold side, thereby deteriorating the transfer accuracy. There is a problem that a transfer failure occurs.

  On the other hand, in pattern transfer technology using nanoimprint technology, optical nanoimprint is suitable from the viewpoint of improving throughput and mass production. This is because thermal nanoimprinting requires a process of heating the thermoplastic resin until it is flowable and a cooling process for curing the thermoplastic resin, but optical nanoimprinting does not require a heating process or a cooling process. This is because the transfer time can be shortened and the throughput can be improved. Therefore, it is desired to develop a mold release processing technology that realizes continuous transfer of optical nano-implements corresponding to mass production of microstructures. In particular, when a roller-type pressurization mechanism is used, transfer is performed continuously. However, stopping the transfer every time a transfer failure occurs is the biggest advantage of the roller-type pressurization mechanism. It will damage the sex. Therefore, it is necessary to improve the releasability and transferability that can realize long-time continuous transfer.

  In view of the above technical problems, an object of the present invention is to provide a fine structure transfer apparatus and a fine structure transfer method that can ensure releasability even when repeated continuous transfer is performed and that have excellent transfer accuracy.

  In response to the above problems, the present inventors apply a release agent on the surface of a resin having fluidity before transfer, and always form a fixed amount of a release layer at the interface between the resin and the mold. Perfluoro, which secures releasability, prevents improper transfer due to incomplete releasability, and has a lyophilic part having a functional group reactive with a curable fluid as a releasant applied on the resin surface. It has been found that by using a compound or a siloxane compound, adhesion of a release agent to the mold surface can be suppressed, leading to the present invention.

  That is, the present invention provides a microstructure forming apparatus for transferring a microstructure formed on a mold surface to a resin on a substrate, a curable fluid coating mechanism for coating a curable fluid on the substrate, and the curable composition described above. A release layer forming mechanism on the curable fluid for applying a release agent on the fluid to form a release layer, a pressure mechanism for pressing the curable fluid on the mold, and a mold on the curable fluid A fluid curing mechanism for curing the curable fluid in a state where the curable fluid is pressed, and the release agent has a lyophilic part having a functional group reactive with the curable fluid as a terminal. It is characterized by being a perfluoro compound or a siloxane compound.

  Further, in a microstructure transfer method for transferring a microstructure formed on a mold surface to a resin on a substrate, a curable fluid coating step for applying a curable fluid on the substrate, and the curable fluid on the curable fluid A step of applying a release agent to the substrate, a step of curing the curable fluid with the mold pressed against the curable fluid via the release agent, and a curable fluid cured from the mold. And a perfluoro compound or a siloxane compound having a lyophilic part having a functional group having reactivity with the curable fluid as a terminal is used as the release agent.

  According to the present invention, it is possible to provide a fine structure transfer apparatus and a fine structure transfer method that can ensure releasability even when repeated continuous transfer is performed and that is excellent in transfer accuracy.

1 is a schematic view of a fine structure transfer apparatus of the present embodiment. 1 is a schematic view of a fine structure transfer apparatus of the present embodiment. 1 is a schematic view of a fine structure transfer apparatus of the present invention. Schematic of the fine structure transfer apparatus by a comparative example. 1 is a schematic view of a fine structure transfer apparatus according to the present embodiment. 1 is a schematic view of a fine structure transfer apparatus according to the present embodiment.

  The present invention relates to a microstructure forming apparatus that transfers a microstructure formed on a mold surface to a resin on a substrate. The microstructure transfer device of the present invention includes a curable fluid coating mechanism for coating a curable fluid on a substrate, and a curability for coating a release agent on the curable fluid to form a release layer. Release mechanism for forming a release layer on the fluid, a pressure mechanism for pressing the curable fluid against the mold, and fluid curing for curing the curable fluid in a state where the mold is pressed against the curable fluid. And the release agent is a perfluoro compound or a siloxane compound having a lyophilic part having a functional group having reactivity with the curable fluid at the end.

  The microstructure transfer device of the present invention applies a release agent on the surface of a resin (curing fluid) having fluidity before transfer, and always forms a fixed amount of release layer at the interface between the resin and the mold. By doing so, it is possible to ensure releasability and prevent transfer failure due to releasability. Further, as a mold release agent to be applied on the resin surface, a perfluoro compound or a siloxane compound having a lyophilic part having a functional group having reactivity with the curable fluid at the terminal is used to release the mold release agent on the mold surface. It suppresses adhesion.

Here, the following points are important when a release agent is applied on the surface of the resin having fluidity and a constant amount of the release layer is always formed at the interface between the resin and the mold.
(1) To prevent aggregation of the release agent applied on the surface of the resin.
(2) Forming a release layer on the surface of the resin while suppressing impregnation of the release agent into the resin.
(3) Suppressing adhesion and accumulation of the release layer formed on the resin surface to the mold surface.

  Regarding the above (1), when a perfluoro compound or a siloxane compound used as a release agent is applied on the surface of a resin having fluidity, the release agent tends to aggregate due to low affinity with the resin. The release layer cannot be uniformly formed on the surface of the resin, which causes a transfer defect due to variation in release properties. Regarding (2) above, for example, when a release agent component excellent in compatibility with the resin is used, the release agent component is impregnated in the resin, and the interface between the resin and the mold is formed. Such a release agent component is contrary to the object of the present invention because there is not enough release agent. With regard to (3) above, it is possible to ensure releasability by always forming a certain amount of release layer between the resin and the mold, but the release layer adheres to the mold side, This is because the transfer accuracy is deteriorated as the amount of accumulated is increased.

On the other hand, in the present invention, a perfluoro compound or a siloxane compound having a parent fluid part having a functional group having reactivity with a resin (curable fluid) at the terminal is used. The parent fluid part having a functional group having reactivity with the resin has high affinity with the resin. On the other hand, since the perfluoro compound and the siloxane compound have low affinity with the resin, the release agent of the present invention has a structure in which the parent fluid portion having high affinity with the resin and the lyophobic portion having low affinity with the resin are combined. It is characteristic that it has.
When the release agent of the present invention is applied to a resin having fluidity, the parent fluid portion at the end of the perfluoro compound or the siloxane compound is dispersed in the resin surface layer, and the lyophobic portion on the other end side is the outermost portion of the resin. It becomes a state of being unevenly distributed on the surface. Here, when the parent fluid portion is dispersed in the resin, the release agent is easily fixed, and aggregation of the release agent can be prevented. Moreover, since the structure of the mold release agent is configured such that one end is a parent fluid part and the other end is a lyophobic part, the resin does not impregnate the resin. Furthermore, since the lyophilic portion dispersed in the resin has a functional group reactive with the resin, it reacts with the resin by a curing reaction of the resin. By this reaction, the release layer formed on the resin is firmly bonded to the resin. Thereby, it becomes possible to suppress that the release layer on the resin adheres to the mold side.

  In contrast to the above (1), if a release agent is unevenly distributed on the surface of the resin after the release agent is applied to the surface of the resin having fluidity, the surface of the resin is provided. It is preferable because the release layer can be more uniformly formed.

Further, in order to ensure mold releasability, a mold release layer forming mechanism for forming a release layer on the surface of the mold during or after the transfer process may be provided.
At this time, in order to prevent an unnecessary release layer from being formed on the mold surface, the concentration of the release agent supplied to the mold surface is made lower than when a release layer is previously formed on the mold surface. It is desirable.

  Hereafter, each structure of the fine structure transfer apparatus of this invention is demonstrated.

(mold)
The mold of the present invention has a fine structure (uneven pattern) formed on the surface, and transfers the fine structure to the resin of the transfer object. The mold used in the roller type pressing device is not particularly limited as long as it is processed into a columnar shape or a cylindrical shape and has a fine structure formed on a roll surface that has strength and can be rotated by a central axis. . Alternatively, a fine structure formed on a flexible base material may be wound around a columnar or cylindrical roll. The pattern can be formed by directly cutting the cylindrical roll surface, forming a resist pattern on the roll surface, etching, forming an aluminum film on the roll surface by vapor deposition or sputtering, and then forming an anode. The thing etc. which formed the pore by the oxidation method are illustrated. Furthermore, it is also possible to use a sheet in which a fine pattern is formed on the surface of a resin film by a nanoimprint method or a master mold in which a fine pattern is formed and a Ni replica formed by a Ni electroforming method wound on a roll surface. it can.

  The mold surface of the present invention is preferably subjected to a mold release treatment in advance. The mold release layer on the mold surface is not particularly limited as long as it is a mold release agent composed of a part that bonds with the mold surface and a part that easily exhibits mold release properties. Examples of the portion bonded to the mold surface include -Si-OR (R: alkyl group), -Si-OH, -Si-X (X: halogen element). Fluorine compounds and silicone compounds are preferred as the part that easily exhibits releasability. Specifically, fluoroalkylsilane, LS-160, LS-912, LS-1465, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL (manufactured by Daikin Industries, Ltd.), Novec EGC-1720 (manufactured by Sumitomo 3M Company). , Aqua Forb CF, Aqua Forb CM (manufactured by Gelest) and the like. The mold release layer can be formed by diluting these mold release agents in a predetermined diluent and then immersing, drying, rinsing and baking the mold.

(Base material)
The substrate of the present invention is a support substrate for holding a curable fluid. In order to improve productivity, in the case of continuously supplying a base material coated with a curable fluid to a pressurizing mechanism using a belt-like base material, a flexible material is used as the base material. preferable. Furthermore, it is desirable that light can be transmitted in the step of curing the curable fluid, and it is preferable to use a transparent material. Specific examples include acrylic resins, polycarbonates, styrene resins, polyesters, cellulose resins (such as triacetyl cellulose), polyolefins, and alicyclic polyolefins. It is particularly preferable that the base material has been pretreated for improving the adhesion to the curable fluid.

(Curable fluid)
The curable fluid of the present invention is a photocurable resin containing a polymerizable compound having a polymerizable functional group in the structure and a polymerization initiator.

  Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.

  The reactive polymer means a polymer having a molecular weight of 500 or more and having a plurality of reactive functional groups. Specifically, those having one or more reactive functional groups in the skeleton such as (meth) acrylate group or vinyl group, epoxy group or oxetanyl group are preferable. Specifically, poly (meth) acrylate, ethoxylated bisphenol A acrylate, aromatic urethane acrylate, aliphatic urethane acrylate, polyester acrylate, polyethylene terephthalate, polystyrene, polycarbonate, acrylic modified alicyclic epoxide, bisphenol A Examples include epoxides, hydrogenated bisphenol A epoxides, bisphenol F epoxides, novolac epoxides, aliphatic cyclic epoxides, naphthalene epoxides, biphenyl epoxides, and bifunctional alcohol ether epoxides.

  Monomer components include phenoxy glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and methoxytriethylene glycol (meth) acrylate as materials having (meth) acrylate groups or vinyl groups at the terminals. , Methoxypolyethylene glycol (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, isostearyl (meth) acrylate, Lauryl (meth) acrylate, polyethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate , Propoxylated bisphenol A di (meth) acrylate, 1,10-decanediol di (meth) acrylate, cyclodecane dimethanol di (meth) acrylate, ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, 2hydroxy 3 acryloxypropyl methacrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, Dipropylene glycol diacrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, reethylene glycol di ( Acrylate), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated trimethylolpropane tri (meth) acrylate, trimethyl pool propane tri (meth) acrylate, propoxy Trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Examples include, but are not limited to, pentaerythritol hexa (meth) acrylate. If the viscosity at room temperature is low and an acrylate group or a methacrylate group is formed at the molecular chain terminal, it can be basically used in the present invention. In addition, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclopentenyl (meth) acrylate, adamantchel (meth) acrylate, and the like can be given. Moreover, as what has an epoxy group at the terminal, low molecular weight alicyclic epoxide, bisphenol A epoxide, hydrogenated bisphenol A epoxide, bisphenol F epoxide, novolac epoxide, aliphatic cyclic epoxide, naphthalene epoxide, Biphenyl type epoxide, bifunctional alcohol ether type epoxide 1,6-hexanediol glycidyl ether, 1,4-butanediol glycidyl ether and the like are exemplified. Examples of those having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 3-ethyl-3- (phenoxymethyl). Oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl } Examples include oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like. Furthermore, the organic component having a vinyl group includes ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, isophthalic acid. Examples include di (4-vinyloxy) butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyltrimethylolpropane trivinyl ether succinate, 2-hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether and the like. The As mentioned above, although the monomer component which has any functional group of an epoxy group, an oxetanyl group, and a vinyl ether group was illustrated, it is not limited. Any epoxy group, oxetanyl group, or vinyl ether group formed in the molecular chain and having a low viscosity at room temperature can be basically used in the present invention.

  In addition, a crosslinkable reactive diluent component may be included, specifically, N-vinylpyrrolidone, acryloylmorpholine, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropyl. Examples include acrylamide, vinyl (meth) acrylate, allyl (meth) acrylate, methallyl (meth) acrylate, and the like. In particular, vinyl (meth) acrylate is preferable because of its excellent film formability. In addition, examples of the reactive diluent having an epoxy group include acrylic glycidyl ether, alkylphenol monoglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether.

The curable fluid of the present invention contains a reaction initiator for reacting these components in addition to the reactive high molecular weight component and monomer component. The reaction initiator is not particularly limited as long as it initiates the reaction of the reactive group. Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-mori Forinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl Phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) -pheny Phosphine oxide, bis (eta ^{5-2,4-cyclopentadiene-1-yl)} - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl), such as titanium (meth) acrylic Examples thereof include a photopolymerization initiator that initiates a reaction of a group and a vinyl group by light irradiation. These can be applied alone, but can also be used in combination of two or more. In addition, it can also be applied in combination with known photopolymerization accelerators and sensitizers. In addition, as a reaction initiator for initiating the reaction of epoxy group and oxetanyl group, iron-allene complex compound, aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt, pyridinium salt, aluminum complex / silyl ether, proton acid And Lewis acid. Specific examples of the cationic polymerization initiator that starts curing by ultraviolet rays include IRGACURE 261 (manufactured by Ciba Geigy), Optmer S P-150 (manufactured by Asahi Denka Kogyo Co., Ltd.), and Optmer S P-151 manufactured by Asahi Denka Kogyo Co., Ltd. ), Optmer SP-152 (Asahi Denka Kogyo Co., Ltd.), Optmer SP-170 (Asahi Denka Kogyo Co., Ltd.), Optmer SP-171 (Asahi Denka Kogyo Co., Ltd.), Optomer SP-172 (Asahi Denka Kogyo Co., Ltd.), UVE-1014 (manufactured by General Electronics Co., Ltd.), CD-1012 (manufactured by Sartomer), Sun Aid SI-60L (manufactured by Sanshin Chemical Industry), Sun Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun Aid SI-100L ( Sanshin Chemical Industry Co., Ltd.), Sun-Aid SI-110 (Sanshin Chemical Industry Co., Ltd.), Sun-Aid SI-180 (Sanshin Chemical Industry Co., Ltd.) CI-2064 (manufactured by Nippon Soda Co., Ltd.), CI-2639 (manufactured by Nippon Soda Co., Ltd.), CI-2624 (manufactured by Nippon Soda Co., Ltd.), CI-2481 (manufactured by Nippon Soda Co., Ltd.), Uvacure 1590 (Daicel UCB), Uvacure 1591 (Daicel UCB), RHODORSILPhotInIterator 2074 (Rhone-Poulein), UVI-6990 (Union Carbide), BBI-103 (Midori Chemical), MPI-103 (Midori Chemical), TPS-103 (Midori) Chemical Co., Ltd.), MDS-103 (Midori Chemical Co., Ltd.), DTS-103 (Midori Chemical Co., Ltd.), NAT-103 (Midori Chemical Co., Ltd.), NDS-103 (Midori Chemical Co., Ltd.), CYRAURE UVI 6990 (Union Car) Byte Japan). These polymerization initiators can be applied alone, but can also be used in combination of two or more. In addition, it can also be applied in combination with known polymerization accelerators and sensitizers.

(Curing fluid application mechanism)
The curable fluid coating mechanism of the present invention may be any device that can apply a curable fluid with a constant thickness on a substrate. Specifically, a cap coater, a slot die coater, a lip coater, a bar coater, An example is a gravure coater.

(Releasing agent applied on curable fluid)
The release agent applied on the curable fluid in the present invention is a perfluoro compound or a siloxane compound having a parent fluid portion having a functional group having reactivity with the curable fluid at the end, and the parent fluid at one end. It is a compound having a body part and a lyophobic body part at the other end.

  Examples of the perfluoro compound include those having a perfluoroalkyl group or a perfluoropolyether group. Examples of the siloxane compound include materials having low surface energy such as polydimethylsiloxane.

  Specifically, 2, 2, 2-Trifluoroethyl acrylate, 2, 2, 3, 3-Tetrafluoropropyl acrylate, Pentafluorobenzyl acrylate, Pentafluorophenyl acrylate, 2, 2, 3, 3, 3-Pentafluoropropyl acrylate 2, 2, 3, 3, 4, 4-Hexafluoro-1, 5-pentyl diacrylate, Hexafluoro-2-methylisopropyl acrylate, Hexafluoroisopropyl acrylate, 1H, 1H-Heptafluorobutyl acrylate, Heptafluoroisopropyl acrylate 2, 2, 3, 3, 4, 4, 5, 5 -Octafluoro-1,6-hexyl diacrylate, 1H, 1H, 5H-Octafluoropentyl acrylate, 2- (Perfluorobutyl) ethyl acrylate, Perfluorocyclohexylmethyl acrylate, 1H, 1H, 7H-Dodecafluoroheptyl acrylate, 1H, 1H, 2H, 2H-Perfluorooctyl acrylate, 1H, 1H-Perfluoro-n-octyl acrylate, 1H, 1H, 9H-Perfluorononyl acrylate, 1H, 1H, 2H, 2H-Perfluorodecyl acrylate, 1H, 1H, 1 Fluoroacrylate compounds such as H-perfluoroundecyl acrylate and these methacrylate compounds, 3-Heptafluoropropyl-1, 2-epoxypropane, 3, 3, 3-Trifluoro-1, 2-epoxypropane, 3- [2- (PERFLUOROHEXYL) ETHOXY] -1,2-EPOXYPROPANE, 3- (2,2,3,3-Tetrafluoropropoxy) -1,2-epoxypropane, 1H, 1H, 2H-Perfluoro- (1,2-epoxy) hexane, 4, 4, 4- Trifluoro-1,2-epoxybutane, 1,4-Bis (2 ′, 3′-epoxypropyl) octafluoro-n-butane, 1,1,1-Trifluoro-2,3-epoxybutane, 2H-Perfluoroethylglycidyl ether, hexafluoroepoxypropane, 3, -Perfluorohexyl-1, 2-epoxypropane, 3-perfluorohexyl-1, 2-epoxypropane, 3- (1H, 1H, 5H-octafluoropentyloxy) -1, 2-epoxypropane, 3- (1H, 1H, 7H-dodecafluoroheptyloxy) -1 , 2-epo Examples include fluoroepoxy compounds such as xypropane, 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane, and the like. In addition, a fluoro compound whose hydroxyl group is a hydroxyl group, a carboxyl group, a vinyl group, or the like can be used. Examples of silicone materials include those in which the lyophilic part is an acrylic group, methacrylic group, epoxy group, hydroxyl group, carboxyl group, vinyl group, polyether group, etc., and the lyophobic part has a polysiloxane structure. Specifically, X-22-173DX, X-22-174DX, X-22-2426, X-22-2475, X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, X-22-176DX, X-22-176F, X-22-4952, X-22-4272, X-22-6266 Chemical)), TSF4730, YX3965, SILWET L-8600, SILSOFT860, SILSOFT900 (above Momentive) and the like. These release agents are dissolved in an organic solvent such as a fluorine-based solvent or ethanol and applied onto the curable fluid. The said mold release agent may use what combined 2 or more types.

(Mechanism for forming release layer on curable fluid)
The release layer formation mechanism on the curable fluid of the present invention is not particularly limited as long as it can be applied thinly and uniformly on the surface of the curable fluid applied on the substrate. Specifically, any spraying agent can be applied from the tip of the nozzle. By making the release agent mist, the release agent can be landed only on the surface layer of the curable fluid, and the release agent can be uniformly sprayed on the entire outermost surface. Further, the release layer forming mechanism on the curable fluid is more preferably one in which a plurality of nozzles are arranged in a row in order to improve the uniformity of the release agent sprayed on the entire outermost surface of the curable fluid. .

(Pressure mechanism)
The pressurizing mechanism of the present invention is a mechanism for pressing the mold against the resin on the substrate. In a parallel plate type pressing apparatus, a mold and a base material are sandwiched between a pair of pressure plates (stages), and are pressed by a pair of pressure plates. Moreover, in a roller-type press apparatus, it is a mechanism which pressurizes with the applied pressure of a pressure roll by supplying a base material between a roll-shaped mold and a pressure roll. The mechanism may be any mechanism that can press the mold against the resin on the substrate, and is not limited thereto.

(Fluid hardening mechanism)
The fluid curing mechanism of the present invention is not particularly limited as long as it is an apparatus capable of applying energy for curing the curable fluid while the curable fluid is pressed against the mold. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, a UV-LED lamp capable of irradiating ultraviolet rays, and the like are exemplified.

(Mold release agent uneven distribution mechanism)
The release agent uneven distribution mechanism of the present invention promotes uneven distribution by applying energy such as heat to the release agent applied on the curable fluid. Specifically, a heating heater, an induction heater, an infrared lamp, etc. are illustrated.

(Mold release layer formation mechanism)
The mold release layer forming mechanism of the present invention is not particularly limited as long as it is a mechanism for applying and fixing the release layer on the mold surface. As a specific application mechanism, a mist-like mold release agent can be applied from the tip of the nozzle, but a mechanism for applying a mold release solution in which the mold release agent is dissolved is exemplified. Examples of the mechanism for fixing the release agent on the mold surface after the release agent is applied include a heating mechanism and an ultraviolet irradiation mechanism. These two mechanisms are combined to form a mold release layer forming mechanism.

  First, the fine structure transfer apparatus and transfer method of this embodiment will be described. FIG. 1 shows a schematic view of a fine structure transfer apparatus of this embodiment. On the backup roll 3 using an on-roll die coater which is a curable fluid coating mechanism 2 on a polycarbonate film having a width of 300 mm and a thickness of 100 μm wound as a base material 1 from a base material winding roll (not shown). A photo-curing type radical polymerization type curable fluid 4 was applied to an area having a coating width of 200 mm so as to have a thickness of 20 μm. At this time, the conveyance speed of the base material 1 was set to 2 m / min. Next, a mixed mist of air and a release agent was applied onto the curable fluid 4 from the curable fluid upper release layer forming mechanism 5 in which four two-fluid nozzles were attached in the substrate width direction. Here, the mold release agent was an HFE7100 (manufactured by 3M) solution containing 0.01 wt% of H, 1H, 2H, and 2H-perfluorodecyl acrylate. As a result, a release layer 6 having an acrylate group as the parent fluid portion 6-1 and a perfluorodecyl group as the loose fluid portion 6-2 was formed on the curable fluid 4 on the curable fluid 4. . In this state, a release layer 6 is formed on the fine structure forming surface of the mold 7 that has been subjected to a release treatment (manufactured by Daikin Industries) with a perfluoropolyether optool on the surface, and the curable fluid 4 on the substrate 1. Was pressed with a pressure roll 8 at a pressure of 0.2 MPa, then exposed and cured with an ultra-high pressure mercury lamp of a fluid curing mechanism 9, and peeled off to produce a fine structure. As the mold 7, a cylindrical mold having a diameter of 100 mm and a pattern area width of 150 mm in which a large number of conical micropores having an upper diameter of about 200 nm and a depth of about 200 nm were previously formed by an anodic oxidation method was used.

  Continuous transfer was performed by the fine structure transfer apparatus of this example. The shape was evaluated by AFM for the formation pattern of each 10 m portion of the manufactured sample. As a result, it was found that a conical pattern having a height of about 200 nm was formed in all evaluation regions. The results are shown in Table 1.

  As shown in FIG. 2, an infrared heater furnace is installed as the release agent uneven distribution mechanism 10 on the downstream side of the release layer forming mechanism 5 on the curable fluid in the same apparatus as in Example 1, and the substrate temperature Was adjusted to 80 ° C. Therefore, the fine structure was transferred using the same material as in Example 1. Continuous transfer was performed by the fine structure transfer apparatus of this example. The shape was evaluated by AFM for the formation pattern of each 10 m portion of the manufactured sample. As a result, it was found that a conical pattern having a height of about 200 nm was formed in all evaluation regions. The results are shown in Table 1.

  As shown in FIG. 3, a two-fluid nozzle similar to the mold release layer forming mechanism on the curable fluid was installed as the mold release layer forming mechanism 11 on the mold upper part of the same apparatus as in Example 2. Next, the fine structure was transferred using the same material as in Example 1. At the time of transfer, a release agent having a concentration of 1/10 of the release agent of the release layer on the curable fluid was applied to the mold surface and heated to form a release layer. Continuous transfer was performed by the fine structure transfer apparatus of this example. The shape was evaluated by AFM for the formation pattern of each 10 m portion of the manufactured sample. As a result, it was found that a conical pattern having a height of about 200 nm was formed in all evaluation regions. The results are shown in Table 1.

  Using the same apparatus as in Example 1, the fine structure was transferred. At that time, a 0.01 wt% MEK (Methyl Ethyl Ketone) solution of X-22-2475 which is methacryl-modified silicone was used as a release agent to be applied onto the curable fluid. Continuous transfer was performed by the fine structure transfer apparatus of this example. The shape was evaluated by AFM for the formation pattern of each 10 m portion of the manufactured sample. As a result, it was found that a conical pattern having a height of about 200 nm was formed in all evaluation regions. The results are shown in Table 1.

  Using the same apparatus as in Example 1, the fine structure was transferred. At that time, a 0.01 wt% MEK solution of X-22-2475 which is methacryl-modified silicone is used as a release agent to be applied onto the curable fluid, and a photocationically polymerizable epoxy resin composition is used as the curable fluid. It was. Therefore, continuous transfer was performed by the microstructure transfer apparatus of the present invention. The shape was evaluated by AFM for the formation pattern of each 10 m portion of the manufactured sample. As a result, it was found that a conical pattern having a height of about 200 nm was formed in all evaluation regions. The results are shown in Table 1.

[Comparative Example 1]
The continuous transfer of the fine structure was performed with the same apparatus and the material composition of the curable fluid as in Example 1. In that case, it implemented without apply | coating the mold release agent on a curable fluid. As a result, the mold and the curable fluid were in close contact when 10 m was transferred, and transfer could not be continued.

[Comparative Example 2]
The continuous transfer of the fine structure was performed with the same apparatus and the material composition of the curable fluid as in Example 1. At that time, as a mold release agent on the curable fluid, a mold release agent having no parent fluid part was an HFE7100 (manufactured by 3M) solution having a perfluorodecane content of 0.01 wt%. As a result, perfluorodecane gradually deposited on the mold pattern, and the pattern height decreased as the transfer distance increased.

[Comparative Example 3]
As shown in FIG. 4, a heater-added pressure roll in which a polycarbonate sheet of 100 μm is used as a substrate, a mold 12 with a heater having a pattern similar to that of Example 1 and a silicone rubber having a thickness of 1 mm is formed on the outer periphery of the roll. 13 was used for pattern transfer at a mold temperature of 180 ° C. and a transfer speed of 2 m / min. As a result, the flowability of the polycarbonate sheet became insufficient, and the pattern height was 10 nm or less.

  In Examples 1 to 5, the throughput can be shortened by applying a roller-type press device using optical nanoimprint, and the release layer on the curable fluid using the release agent of this example. The formation mechanism can provide a fine structure transfer device that is excellent in productivity without causing deterioration in releasability and occurrence of transfer failure even if continuous transfer is performed.

  In addition, although the example which applied the roller-type press apparatus was demonstrated in the above Example, this invention can be applied other than a roller-type press apparatus. For example, as shown in FIG. 5, it is also possible to carry out continuous molding by conveying a substrate every time transfer is completed using a pressurizing mechanism using a flat stage 14 and a mold 7. Moreover, as shown in FIG. 6, after forming the resin layer on the substrate of the single wafer by the curable fluid coating mechanism 2 as well as the apparatus in which the belt-like substrate is continuously sent to the pressurizing mechanism Also, the present invention can be applied to a batch-type apparatus in which the substrate is sequentially moved by a transport mechanism with respect to each mechanism such as the release layer forming mechanism 5 and the pressurizing mechanism.

  The present invention is used in the field of forming a fine structure on the surface, such as biodevices, energy devices, optical components, and recording media.

DESCRIPTION OF SYMBOLS 1 Base material 2 Curable fluid application | coating mechanism 3 Backup roll 4 Curable fluid 5 Curable fluid release layer formation mechanism 6 Release layer 6-1 Parent fluid part 6-2 Sparse fluid part 7 Mold 8 Pressure roll 9 Fluid curing mechanism 10 Release agent uneven distribution mechanism 11 Mold release layer forming mechanism 12 Heater mold 13 Heater additional pressure roll 14 Stage

Claims (19)

In the fine structure forming device that transfers the fine structure formed on the mold surface to the resin on the substrate,
A curable fluid application mechanism for applying a curable fluid on a substrate;
Applying a release agent on the curable fluid, and forming a release layer on the curable fluid,
A pressure mechanism for pressing the curable fluid against the mold;
A fluid curing mechanism for curing the curable fluid in a state where a mold is pressed against the curable fluid; and
The microstructure transfer apparatus, wherein the release agent is a perfluoro compound or a siloxane compound having a parent fluid part having a functional group having reactivity with the curable fluid at the end.   2. The microstructure transfer device according to claim 1, wherein the base material is a strip-like flexible film, the mold is in a roll shape, and the resin on the base material is finely continuously while rotating the mold. A fine structure transfer apparatus for transferring a structure.   2. The microstructure transfer apparatus according to claim 1, wherein the curable fluid is a photocurable resin composition comprising a compound having a polymerizable functional group and a photoreaction initiator. apparatus.   4. The microstructure transfer apparatus according to claim 3, wherein a lyophilic portion of the release agent has the same functional group as the polymerizable functional group.   2. The fine structure transfer apparatus according to claim 1, wherein the perfluoro compound is a perfluoroalkyl compound or a perfluoropolyether compound.   2. The microstructure transfer device according to claim 1, wherein the release layer forming mechanism on the curable fluid forms the release agent in an aerosol form and is applied onto the curable fluid. apparatus. The fine structure transfer apparatus according to claim 1,
A microstructure transfer apparatus having a mold release layer forming mechanism for forming a release layer on the surface of the mold.   8. The microstructure transfer apparatus according to claim 7, wherein a release layer is formed in advance on the surface of the mold.   9. The fine structure transfer apparatus according to claim 8, wherein the release layer previously formed on the mold surface has a perfluoropolyether structure.   2. The microstructure transfer apparatus according to claim 1, further comprising a release agent uneven distribution mechanism that unevenly distributes a release layer on a surface portion of the curable fluid.   11. The microstructure transfer apparatus according to claim 10, wherein the release agent uneven distribution mechanism is a mechanism for heating a release layer on the curable fluid. In the fine structure transfer method of transferring the fine structure formed on the mold surface to the resin on the substrate,
A curable fluid application step of applying a curable fluid on the substrate;
Applying a release agent on the curable fluid;
Curing the curable fluid in a state where the mold is pressed against the curable fluid via the release agent;
Separating the cured curable fluid from the mold, and
The microstructure transfer method, wherein the release agent is a perfluoro compound or a siloxane compound having a parent fluid part having a functional group having reactivity with the curable fluid at the end.   13. The microstructure transfer method according to claim 12, wherein the curable fluid is a photocurable resin composition comprising a compound having a polymerizable functional group and a photoreaction initiator. Method.   14. The fine structure transfer method according to claim 13, wherein the parent fluid part of the release agent has the same functional group as the polymerizable functional group.   13. The microstructure transfer method according to claim 12, wherein the base material is a strip-like flexible film, the mold is a roll, and the resin on the base material is finely continuously while rotating the mold. A fine structure transfer method characterized by transferring a structure.   13. The microstructure transfer method according to claim 12, wherein the perfluoro compound is a perfluoroalkyl compound or a perfluoropolyether compound.   13. The fine structure transfer method according to claim 12, wherein a release layer is formed in advance on the mold.   13. The microstructure transfer method according to claim 12, further comprising the step of unevenly distributing the release agent on the surface portion of the curable fluid after the step of applying the release agent. Method.   19. The microstructure transfer method according to claim 18, wherein the release agent of the curable fluid is heated to make the release agent unevenly distributed.