JP6371076B2 - Method for producing film mold - Google Patents

Description

The present invention relates to the production how the film-like mold.

  Conventionally, in the field of nanoimprint, in order to shape a fine structure in an optical element, a mold having a fine structure formed in advance is used, and the fine structure of this mold is applied to the surface of a glass substrate, a plastic substrate, a plastic film or the like. (See Patent Document 1 and Patent Document 2).

  As a method of transferring the fine structure of the mold, a mold on which a fine pattern such as fine grooves and holes is formed is an original plate (also called a mold or a template), and the fine pattern of the original plate is pressed against the material to be transferred. For example, and a method for transferring a fine pattern of an original plate against a thermoplastic resin. In addition, a so-called UV nanoimprint, a method of applying a photocurable resin on a fine pattern of an original plate or a transfer material and performing phototransfer (refer to Patent Document 3) has also been proposed. In these methods, the resolution of the fine structure transferred to the transfer material is determined by the precision of the fine pattern formed on the original. For this reason, if a mold in which a highly accurate fine pattern is formed can be manufactured, the microstructure can be transferred with an inexpensive apparatus by repeatedly using the mold. As a mold used as an original plate, a parallel plate type mold (also called a wafer or a plate) and a cylindrical (roller) type roll-shaped mold are generally known (see Patent Document 4 and Non-Patent Document 1).

  Most of the molds described above are made of silicon, glass, aluminum, or nickel made from an electroforming method. However, in recent years, a manufacturing method and a transfer device using a film mold have been developed (Patent Document 5 and Patent Document 6). The film-shaped mold is extremely useful because the transfer material is not flat and macro waviness can be transferred following the waviness. That is, if a film-like mold is used, it is possible to mold the curved surface of the lens surface or mold a substrate having a sapphire substrate or the like.

  The film mold is produced from an original plate made of silicon, glass, or aluminum. For example, an original fabric roll having a fine pattern formed on the peripheral surface is prepared. Moreover, UV photocurable resin is apply | coated to the surface of a film-form base material. The UV photocurable resin is transferred by pressing a fine pattern of the raw roll. Thereafter, the UV light curable resin is cured by UV light irradiation, and the UV light curable resin layer (resin cured material layer) is peeled from the raw fabric roll to obtain a film-shaped mold. Thus, by replicating a number of film-shaped molds from one original plate, the cost of producing the original plate can be absorbed.

  Fluorine-containing polymerizable materials and fluorine-based surfactants such as fluorine-containing surfactants are included in the UV photocurable resin used for the production of the film mold, and the separation from the original plate is reduced due to the decrease in surface free energy caused by fluorine atoms. Materials that can realize transfer with good moldability have been developed (Patent Documents 6 and 7).

  A production facility and a production method capable of producing a final product or replicating a film mold by lamination from a film mold have also been proposed (Patent Document 8).

US Pat. No. 5,259,926 US Pat. No. 5,772,905 JP 2005-238719 A JP 2006-5022 A JP 2011-20272 A International Publication No. 2009/125697 Pamphlet JP 2010-83970 A Special table 2010-525968 gazette

Hua Tan, Andrew Gibertson, Stephen Y. Chou, “Roller nanoimprint lithography”. Vac. Sci. Technol. B16 (6), 3926 (1998)

  In the transfer apparatus and transfer method using the sheet-shaped mold described in Patent Document 5, when the photocurable resin applied to the transfer material and the sheet-shaped mold are bonded together, the transfer unevenness at the time of bonding is eliminated. Go through the vacuum system. In addition, when the vacuum system is used, it takes time for deaeration and intake, so it is necessary to temporarily stop the conveyance path. In other words, since the conveyance is stopped at each transfer, not only the productivity does not increase, but it is necessary to newly introduce a large and expensive transfer apparatus having such a vacuum facility and a conveyance control system.

  On the other hand, in the mold using the fluororesin described in Patent Document 6, since it is necessary to heat and press above the glass transition temperature at the time of transfer, only batch-type transfer of single wafers is suitable, and a heating and cooling process is required. Inferior to productivity. Moreover, even if it is a photocurable fluorine resin mold, it is a single wafer type, and if it does not wind on a cylinder, it cannot be utilized as a metal mold | die. In this case, there is a problem that a seam is formed, and the resin to be transferred stays at the seam portion, resulting in poor curing or a cause of a gauge band.

  The resin to be transferred described in Patent Document 7 contains a fluorosurfactant or a release agent in advance, thereby improving the release from the mold during transfer, and the high heat resistance of the microstructure after transfer. It contributes to. However, the use of this microstructure as a film mold has not been studied.

  The manufacturing facility or manufacturing method described in Patent Literature 8 is assumed to have a relatively large uneven structure such as a flooring material or wallpaper. Therefore, the viscosity of the material used is 0.2 to 5 Pa · sec (Pascal · sec), and there is a problem in continuous nanostructure transfer due to its filling property.

  By the way, when a film-shaped mold is produced using a photocurable resin containing a fluorine-containing substance, and a new film-shaped mold is duplicated using this film-shaped mold as a master, a conventional method for producing a film-shaped mold Then, bubbles were generated, and the transfer of the fine uneven structure sometimes failed.

The present invention has been made in view of the problems described above, and an object thereof is to provide a manufacturing how excellent film-like mold transfer releasability.

  As a result of intensive research in order to solve the above problems, the present inventor has produced a film mold using a photocurable resin containing a fluorine-containing substance, and newly uses this film mold as an original plate. When replicating a film-like mold, it was found that bubbles may be generated and the transfer of the fine concavo-convex structure may not be successful, and the present invention has been made based on this finding. That is, the present invention is as follows.

The method for producing a film-shaped mold in the present invention comprises a mold substrate and a cured resin layer provided on the surface of the mold substrate, and the cured resin layer is formed on the surface of the mold substrate. , A photocurable resin layer formed by applying a photocurable resin containing a fluorine-containing substance, the photocurable resin layer is bonded to a fine uneven structure of an original plate, and the photocurable resin is applied to the original plate A step of preparing a (n-1) th film-shaped mold (n is an integer of 2 or more) formed by photocuring the photocurable resin layer while pressing the layer; A step of applying a photocurable resin having a viscosity of 50 mPa · sec or less on the surface to form a transferred resin layer, and a surface on which the inverted structure of the fine uneven structure of the cured resin layer is formed, Bonding the transferred resin layer of the transferred substrate A step of photocuring the transferred resin layer by irradiating light in a state where the cured resin layer and the transferred resin layer are in contact with each other; and (n− 1) releasing the film-shaped mold to obtain an n-th film-shaped mold, and the fine concavo-convex structure has a nano-sized pitch, and the first from the bonding point to the mold release point. When the transport distance of the film mold of (n-1) is d1, and the transport distance of the nth film mold is d2, [(d2-d1) / (average distance between d1 and d2)] × 1000000 (Ppm) is in the range of 0 ppm to 3000 ppm, and the transport distances d1 and d2 are 0.1 m to 1.5 m.

  With this configuration, it is possible to suppress the generation of bubbles as compared with the prior art from the pasting step to the photocuring step and the mold releasing step, and it is possible to realize good transferability.

  In the method for producing a film-shaped mold of the present invention, a fluorine element concentration (Es) of a surface layer on which the fine concavo-convex structure of the cured resin layer of the n-1st film-shaped mold is formed is the cured resin layer. It is characterized by being higher than the average fluorine concentration (Eb).

  In the method for producing a film-shaped mold of the present invention, the n is 2, and the original plate is a cylindrical mold.

  In the method for producing a film-shaped mold according to the present invention, a release treatment is performed on the surface of the cylindrical mold.

  In the method for producing a film-shaped mold of the present invention, the step of applying a photocurable resin to the surface of a film-shaped transferred substrate to form a transferred resin layer, and the fine uneven structure of the cured resin layer In place of the step of bonding the transferred resin layer of the transferred substrate to the formed surface, a photocurable resin is applied to the surface of the cured resin layer on which the fine uneven structure is formed. Forming a transferred resin layer, and bonding the transferred resin layer to the surface of a film-like transferred substrate.

  According to the present invention, when the nth film mold is produced, each transport distance from the point where the (n-1) film mold and the nth film mold are bonded to the point where the mold is released. Therefore, it is possible to eliminate the inclusion of bubbles as compared with the conventional case, and it is possible to prevent transfer defects of the fine concavo-convex structure.

It is a section schematic diagram and a plane schematic diagram of the 1st film mold used for a manufacturing method of a film mold concerning this embodiment. It is the schematic which shows the manufacturing apparatus used for the manufacturing method of the film-form mold in the past. It is the schematic which shows the manufacturing apparatus used for the preparation process of the 1st film mold which concerns on this Embodiment. It is the schematic which shows the manufacturing apparatus used for the duplication process of the 2nd film mold which concerns on this Embodiment. It is the schematic which shows the manufacturing apparatus used for the duplication process of the 2nd film mold which concerns on this Embodiment, and a part different from FIG. It is explanatory drawing which shows the manufacturing method of the nth film mold which concerns on this Embodiment.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  A method for manufacturing the film mold according to the present embodiment will be described. A roll-to-roll method is used for the method for manufacturing the film-shaped mold according to the present embodiment. As the mold, a film mold is used. Hereinafter, a film mold as a mold is described as a first film mold, and a film mold replicated from the first film mold is described as a second film mold.

  The first film-like mold can be manufactured by a roll-to-roll method using a cylindrical mold as an original plate. First, a photocurable resin is applied to the surface of a film-like substrate for the first film-like mold (hereinafter referred to as a mold substrate) to form a photocurable resin layer. The fine concavo-convex structure provided on the peripheral surface of the cylindrical mold is brought into close contact with the uncured photocurable resin layer, and then the photocurable resin layer is photocured to transfer the fine concavo-convex structure onto the surface. A cured resin layer is formed.

  Here, the “film shape” has a property that the film thickness is extremely thin with respect to the length and width, is flexible, and can be formed into a roll shape.

  In addition, the “fine concavo-convex structure” is a surface structure in which a large number of fine convex portions, a large number of fine concave portions, or a large number of fine convex portions and fine concave portions are formed on the surface, and does not limit the size of the concave and convex portions. However, it is preferably applied to a fine structure having an average pitch between convex portions or an average pitch between concave portions of about several tens of micrometers or less. The lower limit value of the average pitch is about several tens of nanometers, but it can also be applied when a smaller pitch can be realized. The fine concavo-convex structure is preferably provided with a nano-sized pitch. “Nanosize” refers to about 1000 nm or less. The scale may be other than the pitch (the size, diameter, depth, etc. of one fine structure). A random structure can be one of the fine structures.

  The fine concavo-convex structure is a pillar shape including a plurality of convex portions having a rectangular shape, a conical shape, a pyramid shape or an elliptical cone shape, or a hole shape including a plurality of concave portions having a conical shape, a pyramid shape or an elliptical cone shape, a long hole shape, Alternatively, a line and space shape can be used. Here, the “pillar shape” is a “shape in which a plurality of columnar bodies (conical states) are arranged”, and the “hole shape” is a “shape in which a plurality of columnar (conical) holes are formed”. is there.

  FIG. 1 is a schematic cross-sectional view and a schematic plan view of a first film-shaped mold used in the method for producing a film-shaped mold according to the present embodiment. FIG. 1A shows a schematic cross-sectional view, and FIG. 1B shows a schematic plan view.

  As shown in FIG. 1, the first film mold 1 includes a mold base 11 and a cured resin layer (photo-curable resin layer) 12 formed on the surface of the mold base 11. The The mold base 11 is in the form of a film and is made of a material having excellent flexibility. Although it does not limit, the thickness of the mold base material 11 is about 25 micrometers-200 micrometers. As shown in FIG. 1A, the surface 11a of the mold base 11 is formed as a flat surface.

  As shown in FIG. 1A and FIG. 1B, the cured resin layer 12 formed on the surface of the mold base 11 is cut on both sides, and the width dimension of the cured resin layer 12 is the width of the mold base 11. It is formed smaller than the width dimension. This is because, when a transferred resin layer equivalent to the width of the mold base 11 is formed, the transferred resin layer spreads by the die and bonding pressing, exceeds the width of the mold base 11, Go around the edge or back. This is because the cured resin layer that has been photocured after that may be mixed into the area of the fine concavo-convex structure as a contaminant contamination source. Moreover, although the thickness of the resin cured material layer 12 is based also on the size of a fine uneven structure, it is about 500 nm-5000 nm including a fine uneven structure.

  As shown in FIG. 1A, a fine uneven structure 12 a is formed on the surface of the cured resin layer 12. In FIG. 1B, the fine relief structure 12a is omitted.

  In the present embodiment, the first film mold 1 is used as a mold, and the second film mold is manufactured. A photocurable resin is applied to the surface of the mold substrate of the second film mold to form a photocurable resin layer. The fine concavo-convex structure 12a provided on the surface of the first film mold 1 is brought into close contact with the uncured photocurable resin layer, and then the photocurable resin layer is photocured to form a fine concavo-convex structure on the surface. A transferred resin layer to which is transferred is formed.

  This inventor is a resin layer to be transferred from a point (bonding point) at which the transferred resin layer, which is a photocurable resin layer, and the first film mold are bonded when the second film mold is manufactured. Can be photocured to obtain fine concavo-convex shape with high accuracy without generating air bubbles until the point (release point) where the first film-shaped mold and the second film-shaped mold are peeled off. I found a configuration that can do this.

  FIG. 2 is a schematic view showing a production apparatus used in a conventional method for producing a film mold. FIG. 2A is a schematic diagram showing from a bonding point to a mold release point of the manufacturing apparatus, and FIG. 2B is a schematic diagram showing an enlarged back roll portion.

  As shown in FIG. 2A, conventionally, in the bonding process, a back roll 301 is disposed at a position facing the light source 300, and a first film mold 302 and a second film mold 303 are arranged on the peripheral surface of the back roll 301. Were transported in close contact with each other. However, in this configuration, bubbles may enter from both ends of the film mold from the bonding point a to the mold release point b between the first film mold 302 and the second film mold 303. There was a problem.

  Here, the back roll 301 is a combination of the nip rolls 304 and 305, and changes the conveying direction while bringing the first film mold 302 and the second film mold 303 into close contact with the peripheral surface of the back roll 301. The roll which can ensure the light irradiation area from the light source 300 with respect to the 2nd film mold 303 is pointed out.

As shown to FIG. 2A, the back roll 301 exists between the bonding point a and the mold release point b. Therefore, when the second film mold 303 is brought into close contact with the back roll 301 with the first film mold 302 interposed therebetween, the transport distance d1 of the first film mold 302 and the second film mold 303 are set. The transport distance d2 is different. The transport distance d1 of the first film mold 302 and the transport distance d2 of the second film mold 303 are expressed by the following equations, respectively.
d1 = L1 + 2 (r + t) π × (θ / 360) + L2
d2 = L1 + 2 (r + 2t) π × (θ / 360) + L2
L1: Distance from the bonding point a to the back roll 301 (see FIG. 2A)
r: radius of the back roll 301 (see FIG. 2B)
t: thickness of the film mold (see FIG. 2B)
θ: Holding angle at which the back roll 301 and the film mold are in close contact (see FIG. 2B)
L2: Distance from the back roll 301 to the release point b (see FIG. 2A)

  As shown to FIG. 2A, L1 of 1st film-like mold 302 located inside from the point (point where it adhered) where the 1st film-like mold 302 and the 2nd film-like mold 303 were pasted together. It is shown by the conveyance distance until the mold substrate comes into contact with the back roll 301. In FIG. 2, the thickness t of the film mold is the same for both the first film mold 302 and the second film mold 303. Also, L2 indicates that the first film mold 302 and the second film mold 303 are peeled from the point where the mold base of the first film mold 302 that has been in contact with the back roll 301 is separated from the back roll 301. It is indicated by the transport distance to the point where the two film-shaped molds are separated from each other.

  Further, L1 and L2 can be omitted, and L1 = 0, L2 = 0, or L1 = L2 = 0 can be considered. That is, the bonding point a, the state where the pressing points of the nip roll 304 and the back roll 301 are made the same, the release point b, and the state where the pressing points of the nip roll 305 and the back roll 301 are made the same.

  In FIG. 2B, the first film-shaped mold 302 and the second film-shaped mold 303 are illustrated with a space therebetween for the sake of clarity in the drawing. 302 is in close contact with the back roll 301, and the first film-shaped mold 302 and the second film-shaped mold 303 are in close contact with each other.

  Moreover, when a guide roll exists from the bonding point a to the mold release point b, a term corresponding to the second term of the above formula is added in order to add a transport distance for moving the peripheral surface of the guide roll. This term is required for the number of guide rolls.

  As shown in FIG. 2, when the back roll 301 is introduced between the bonding point a and the release point b, the transport distance d1 of the first film-shaped mold 302 and the second film shape are as shown in the above formula. The conveyance distance d2 of the mold 303 is different. In particular, the transport distance d2 of the second film mold 303 is longer than the transport distance d1 of the first film mold 302. At this time, when the second film-shaped mold 303 is irradiated with light from a position facing the back roll 301, the photocurable resin layer of the photocurable resin layer (transferred resin layer) is photocured in the area. Volume shrinkage occurs. Due to the volume shrinkage of the second film-shaped mold, the uncured photocurable resin layer immediately before photocuring is pulled, and bubbles enter from both ends (ends in the width direction), resulting in transfer failure.

  As described above, since the transport distances d1 and d2 are different in the related art, when the movement amount per unit length accompanying the volume shrinkage is α, the substantial movement amount of the second film mold 303 is α × d2. . At this time, since d1 <d2, since the distance from the bonding point a to the release point b is the same distance without using a back roll (d1 = d2) than the substantial movement amount α × d1 (d2) growing. This substantial amount of movement becomes strain, and bubbles enter from the end to absorb the strain.

  In addition, the first film-shaped mold 302 is in contact with the back roll 301, whereas the mold base material in the second film-shaped mold 303 is the first film mold through the uncured photocurable resin layer. The film-shaped mold 302 is in contact with the surface on which the fine uneven structure is formed. For this reason, in the configuration of FIG. 2, the first film mold 302 that is in close contact with the back roll 301 does not move due to volume shrinkage due to photocuring, so only the uncured photocuring resin layer that has fluidity is present. The air bubbles are easily pulled from both end portions (end portions in the width direction) as much as they are pulled.

  In order to solve these problems, it is conceivable to increase the tension of the second film mold 303. However, as shown in FIG. 2A, the tension is applied by the nip rolls 304 and 305 from the bonding point a to the release point b. Since is in a cut state, the effect cannot be expected.

  Then, it came to solve the said subject by making the conveyance distance from the bonding point of a 1st film-shaped mold and a 2nd film-shaped mold to a mold release point respectively the same.

  That is, by making the transport distance d1 of the first film mold and the transport distance d2 of the second film mold the same, the light due to the volume shrinkage of the photocurable resin layer accompanying the photocuring of the photocurable resin layer. Since the amount of movement of the uncured photocurable resin layer immediately before curing can be reduced, the invasion of bubbles can be suppressed as compared with the conventional case. Specifically, as shown in FIG. 2, when the back roll is used, if the movement amount per unit length is α, the substantial movement amount is α × d2. At this time, since d1 = d2, the substantial movement amounts α × d1 and α × d2 when the distance is the same without using the back roll are substantially the same, and therefore the difference between the substantial movement amounts is small. Therefore, the invasion of bubbles from the end can be suppressed.

  Moreover, when it is set as the same distance without passing through a back roll, since the movement of the first film mold is not restricted as in the case where the back roll exists, the uncured photocurable resin of the second film mold. The first film mold follows the amount of substantial movement of the layer and keeps the first film mold and the second film mold in close contact with each other, effectively suppressing the intrusion of bubbles. Can do.

  Here, the transport distance d1 of the first film mold and the transport distance d2 of the second film mold are the same as [(d2−d1) / (average distance between d1 and d2)] × 1000000 (ppm) Means within the range of 0 ppm to 3000 ppm, and preferably within the range of 0 ppm to 1000 ppm. The transport distances d1 and d2 are about 0.1 m to 1.5 m, and it is preferable that d1 and d2 are the same up to the unit of μm.

  Hereinafter, the manufacturing method of the film mold according to the present embodiment will be described in more detail.

(First film mold production process)
FIG. 3 is a schematic view showing a manufacturing apparatus used in the manufacturing process of the first film mold according to the present embodiment. A manufacturing apparatus 100 shown in FIG. 3 includes an original fabric roll 102 that feeds out a mold base 101 and a take-up roll 104 that winds up a first film mold 103. Between the raw roll 102 and the take-up roll 104, an application means 105 for applying a photocurable resin on the mold base 101 in order from the upstream side to the downstream side in the conveyance direction MD of the mold base 101. A guide roll 106, a cylindrical mold 107 having a fine concavo-convex structure on the outer peripheral surface, a nip roll 108a for bringing the photocurable resin on the mold base 101 into close contact with the outer peripheral surface of the cylindrical mold 107, and The pressing means 108 consisting of 108b, the light source 109 which irradiates light to photocurable resin, and the guide roll 110 are provided.

  In addition, when apply | coating photocurable resin using a solvent, you may further provide the drying furnace 111 which dries the solvent in photocurable resin.

  Using the manufacturing apparatus 100 having the above-described configuration, a first film mold is manufactured as follows. First, a light curable resin layer is formed by applying a light curable resin on the light transmissive film-like mold substrate 101 fed from the raw fabric roll 102 by the applying means 105. The mold base 101 with the photocurable resin layer is supplied to the cylindrical mold 107 through the guide roll 106.

  Next, while rotating the cylindrical mold 107, the pressing means 108 brings the outer peripheral surface of the cylindrical mold 107 into close contact with the photocurable resin layer to transfer the fine concavo-convex structure onto the surface of the photocurable resin layer. Next, the light curable resin layer is irradiated with light from the light source 109 to photocur the photocurable resin layer to form a cured resin layer, and the first film mold 103 is manufactured. The first film-like mold 103 is taken up by the take-up roll 104 through the guide roll 110.

  In addition, in the manufacturing process of the 1st film-shaped mold 103, in order to protect the fine concavo-convex structure transcribe | transferred from the cylindrical metal mold | die 107 to the 1st film-shaped mold 103, on the photocurable resin layer after photocuring. A protective film (cover film) may be laminated.

  In the manufacturing process of the first film mold 103, the cylindrical mold 107 and the photocurable resin layer are in close contact with each other by the pressing means 108 that presses the cylindrical mold 107 and the photocurable resin layer. Light curing is performed by irradiating the photocurable resin layer with light. Since the fine concavo-convex structure on the outer peripheral surface of the cylindrical mold 107 and the photocurable resin layer are in close contact with each other, the fine concavo-convex structure on the outer peripheral surface of the cylindrical mold 107 can be accurately photo-transferred, and oxygen-induced Insufficient curing can be avoided.

  Moreover, in the manufacturing process of the 1st film mold 103, it is preferable to light-irradiate by making the cylindrical metal mold | die 107 and a photocurable resin layer closely_contact | adhere in nitrogen atmosphere. Thereby, contact of oxygen in the atmosphere with the photocurable resin of the photocurable resin layer can be avoided, and inhibition of the photopolymerization reaction by oxygen can be reduced, so that the photocurable resin can be sufficiently cured. Because it can.

  In order to irradiate light by bringing the photocurable resin layer and the cylindrical mold 107 into close contact with each other, the photocurable resin layer and the cylindrical mold 107 are directly pressed by the nip rolls 108a and 108b as the pressing means 108. Then, light may be irradiated. In addition, light may be irradiated in a state where the tension of the mold base 101 is controlled by feeding and winding control and the photocurable resin layer and the cylindrical mold are pressed. In these cases, the pressing pressure and tension can be appropriately adjusted depending on the transferability of the photocurable resin layer.

(Second film mold replication process)
FIG. 4 is a schematic view showing a manufacturing apparatus used in the duplication process of the second film mold according to the present embodiment.

  The manufacturing apparatus 200 shown in FIG. 4 has a first delivery roll (first delivery means) 202 for delivering the transfer substrate 201 and a first film mold 203 for winding the completed second film mold 203. A take-up roll (first take-up means) 204. Also, a second delivery roll (second delivery means) 206 for delivering the first film mold 103 and a second take-up roll (second delivery roll) for winding the first film mold 103 are provided. Winding means) 212. The first feeding roll 202 and the second feeding roll 206 constitute a feeding means 220, and the first winding means 204 and the second winding means 212 constitute a winding means 230.

  As shown in FIG. 4, the feeding means 220 is located on the upstream side of the manufacturing apparatus 200, and the winding means 230 is located on the downstream side of the manufacturing apparatus 200. As shown in FIG. 4, the first film mold 103 is arranged between the delivery means 220 and the winding means 230 in order from the upstream side to the downstream side in the transport direction MD of the first film mold 103. Are provided with a bonding means 207 for bonding and adhering the substrate 201 to be transferred, a light source (light irradiation means) 210 for irradiating light to the photocurable resin layer, and a release means 211. Yes.

  Further, as shown in FIG. 4, between the first feed roll 202 and the bonding unit 207, an application unit 205 that applies a photocurable resin to the surface of the transfer base 201 is provided.

  The bonding means 207 is composed of a pair of laminate rolls 207a and 207b. The bonding unit 207 also serves as a pressing unit.

  The release means 211 is composed of a pair of peeling rolls 211a and 211b. The release means 211 may be defined including not only the peeling rolls 211a and 211b but also the winding rolls 204 and 212.

  Further, when the photocurable resin is dissolved in a solvent and applied to the transfer base material 201, a drying furnace 213 can be provided on the downstream side of the applying unit 205. Further, a drying furnace 214 may be provided on the downstream side of the bonding unit 207.

  Further, the first delivery roll 202 and the second delivery roll 206 may be interchanged. That is, you may apply photocurable resin (transferred resin layer) on the fine uneven structure (unevenness formation surface) formed in the resin cured material layer of the 1st film-form mold 103. FIG.

  Using the manufacturing apparatus 200 having such a configuration, the second film-shaped mold is duplicated as follows.

  First, the substrate 201 to be transferred is fed from the first feed roll 202, and the photocurable resin is directly applied on the surface by the coating means 205 to form a photocurable resin layer. This photocurable resin layer is a transferred resin layer.

  Next, the fine uneven structure (unevenness forming surface) of the cured resin layer of the first film mold 103 unwound from the second delivery roll 206 by the bonding means 207 is converted into light on the substrate 201 to be transferred. Affix to the curable resin layer.

  As shown in FIG. 4, a substrate 201 to be transferred, in which a first film mold 103 and a photocurable resin layer (transferred resin layer) are formed between laminate rolls 207a and 207b constituting the bonding means 207, Pass through. At this time, the photo-curable resin layer on the transferred substrate 201 is pasted into the resin application region of the fine concavo-convex structure (the concavo-convex formation surface) formed on the resin cured product layer of the first film mold 103. The first film-like mold 103 and the transferred substrate 201 can be aligned, for example, by installing a film meandering adjustment device.

  In addition, the first delivery roll 202 and the second delivery roll 206 are interchanged, and the photo-curing property is formed on the fine concavo-convex structure (unevenness forming surface) formed on the resin cured product layer of the first film mold 103. When a resin (transferred resin layer) is applied, in the bonding step, a photocurable resin (transferred resin layer) applied to the surface of the film-like transfer substrate 201 on the first film-like mold 103 side. ).

  The transferred substrate 201 provided with the first film mold 103 and the photocurable resin layer is supplied to a light source 210 which is a light irradiation means (exposure means). At this time, the fine concavo-convex structure (unevenness forming surface) formed on the resin cured product layer of the first film mold 103 is applied to the photocurable resin layer (transferred resin layer) by the bonding unit 207 which also serves as a pressing unit. It can be adhered. In such a close contact state, the light curable resin layer is irradiated with light from the light source 210 to photocur the photocurable resin layer.

  Between the bonding means 207 and the release means 211, the first film-like mold 103 and the transfer target substrate 201 provided with the photocurable resin layer are laminated rolls 207a and 207b and peeling rolls 211a and 211b. The first film mold 103 and the substrate 201 to be transferred can be effectively brought into close contact with each other, the inclusion of bubbles and the uncuring of the photocurable resin layer by oxygen Can be prevented.

  Thereafter, in the mold release means 211, the substrate to be transferred 201 having a cured resin layer (transferred resin layer) formed on the surface from the first film mold 103, that is, the second film mold 203 is removed. Peel off. At this time, the inverted shape of the fine concavo-convex structure formed on the first film mold 103 is transferred to the cured resin layer (transferred resin layer) of the second film mold 203.

  Thereafter, the second film-shaped mold 203 is wound around the first winding roll 204. On the other hand, the first film mold 103 is wound around the second winding roll 212.

  In this Embodiment, as mentioned above, the conveyance distance of the 1st film mold from the bonding point a to the mold release point b and the conveyance distance of the 2nd film mold are made the same. Here, the bonding point a is a point where the first film-shaped mold and the second film-shaped mold (the substrate to be transferred) first come into contact between the laminate rolls 207a and 207b shown in FIG. For example, it is an intersection point between the laminating rolls 207a and 207b and connecting the midpoints of the laminating rolls 207a and 207b in a straight line. The release point b is the first point at which the first film-shaped mold and the second film-shaped roll are separated from each other when the first film-shaped mold and the second film-shaped roll are pulled out from between the separation rolls 211a and 211b. The point of intersection between 211a and 211b when the middle points of the peeling rolls 211a and 211b are connected in a straight line.

  FIG. 5 is a schematic view showing a manufacturing apparatus used in the second film-shaped mold duplication process according to the present embodiment and partially different from FIG. 4. The manufacturing apparatus shown in FIG. 5 is partially different in structure from the bonding means 207 to the release means 211 with respect to FIG. In FIG. 5, the delivery means 220 and the winding means 230 shown in FIG. 4 are omitted.

  Even when the manufacturing apparatus shown in FIG. 5 is used, the transport distance of the first film mold and the transport distance of the second film mold from the bonding means 207 to the release means 211 can be made the same. . By arranging guide rolls 215a and 215b between the bonding means 207 and the release means 211, the transport distance from the bonding means 207 to the release means 211 can be set to the first film mold and the second film. By making the guide rolls 215a and 215b contact the film-shaped mold while keeping the same as the film-shaped mold, the film-shaped mold itself can be photocured in a state avoiding bending and a decrease in tension.

  Here, the guide rolls 215a and 215b do not have a configuration in which the film-shaped mold is sandwiched by a combination with a nip roll unlike the back roll, but indicate a roll having a surface that surrounds only one surface side of the film-shaped mold. In FIG. 5, two guide rolls 215a and 215b are provided. To make the transport distance of the first film mold and the transport distance of the second film mold the same, the first film mold In the second film mold, the distance moved while closely contacting the guide roll 215a and the guide roll 215b is adjusted to be the same as the distance moved while closely contacting the guide roll 215a and the guide roll 215b. do it. For example, an even number of guide rolls having the same radius are prepared, and an equal number of guide rolls in which the film mold moves clockwise on the guide roll and guide rolls in which the film mold moves counterclockwise on the guide roll. The first film-shaped mold transport distance and the second film-shaped mold transport by arranging and making the holding angle θ with respect to the guide roll the same (corresponding to θ in FIG. 2B) for all the guide rolls. The distance can be the same. By changing the holding angle θ and the radius of the guide roll, the arrangement of the guide rolls can be changed, or the guide rolls can be arranged in an odd number. In addition, it is preferable that it is as horizontal as possible from the bonding point a to the mold release point b, and the holding angle θ when the guide roll is provided as shown in FIG. 5 is preferably about 0 ° to 45 °. is there.

  Hereafter, the component of the manufacturing method of the film mold which concerns on this Embodiment is demonstrated in detail.

(Film substrate)
As the mold substrate 101 used in the production of the first film mold and the transfer target substrate 201 used for the duplication of the second film mold, a film substrate having optical transparency can be used.

  The film-like substrate is not particularly limited as long as it is mainly composed of a material that is substantially light transmissive with respect to a light source used in the ultraviolet / visible light region, but has excellent handling properties and workability. A resin material is preferable. Examples of such resin materials include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cycloolefin resin (COP), cross-linked polyethylene resin, polyvinyl chloride resin, polyarylate resin, polyphenylene ether resin, and modified polyphenylene ether resin. , Polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, amorphous thermoplastic resin such as triacetyl cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate resin And crystalline thermoplastic resins such as polyethylene resin, polypropylene resin, polybutylene terephthalate resin, aromatic polyester resin, polyacetal resin, and polyamide resin.

  The film-like substrate is preferably film-like in order to be applied to the roll-to-roll method.

  Although the thickness of a film-like base material is based also on material, Preferably it is 20-200 micrometers, More preferably, it is 50-150 micrometers, More preferably, it is 50-100 micrometers. If it is 200 micrometers or less, the transmittance | permeability of the ultraviolet-ray used for the light source of optical nanoimprint is favorable, and sufficient light quantity for photocuring can be obtained. If it is 20 micrometers, since the rigidity as a film can be hold | maintained, handling is easy.

  The surface of the film-like substrate can be subjected to primer treatment, atmospheric pressure plasma treatment, or corona treatment in order to improve adhesion with the photocurable resin.

  In the film mold manufacturing method according to the present embodiment, as described above, light is applied to the photocurable resin layer in a state of being in close contact with the cylindrical mold 107 or the resin cured product layer of the first film mold 103. Irradiate to light cure. For this reason, although it depends on the photocurable resin to be used, the film-like substrate is required to have good transmittance in the wavelength range of 200 nm to 500 nm. Depending on the photosensitivity of the photo-curable resin used, there is no particular limitation on the specific transmittance value in the wavelength range of 200 nm to 500 nm, but if the 365 nm, 405 nm and total light transmittance are good, light A curable resin is preferable because it is sufficiently photocured. Moreover, if the transmittance | permeability in the wavelength range of 200 nm-500 nm is favorable, the light irradiation energy required for hardening of photocurable resin can be reduced, and the speeding-up of transcription | transfer can be achieved.

(Photo-curing resin)
The photocurable resin layer (resin cured product layer, transferred resin layer) is formed of a photocurable resin. The photo-curing resin is transferability, peelability from the original, adhesion to the film-like substrate, viscosity, film-forming properties, photosensitivity, mechanical properties after curing, and peelability from the resin layer during resin mold preparation. Select with consideration.

  The cured resin layer obtained by photocuring the photocurable resin layer has an average fluorine element concentration (Es) in the surface layer (10 nm or less) on the fine relief structure (unevenness formation surface) side in the photocurable resin layer. It is preferably higher than the fluorine element concentration (Eb).

  According to this, the fluorine element density | concentration (Es) of the fine uneven | corrugated shaped structure side (unevenness formation surface side) in a resin cured material layer is relatively high with respect to the average fluorine element concentration (Eb) in a resin cured material layer. Therefore, for example, when the resin cured product layer of the second film-shaped mold is releasable from the first film-shaped mold, or when the microstructured product developed from the second film-shaped mold is manufactured, The releasability of the microstructured product from the film-shaped mold 2 is improved.

  The fluorine atoms in the cured resin layer are introduced by the fluorine atom-containing material. The fluorine-containing substance refers to a surfactant, a fluorine-containing polymerizable monomer (acrylate, methacrylate, epoxy), a release agent, a surface treatment agent, and a fluorine-based solvent. From the viewpoint of mobility in the photocurable resin, a fluorine-based surfactant and a fluorine-containing polymerizable monomer are preferable.

  In the film mold according to the present embodiment, the fluorine element concentration (Es) in the surface layer of the resin cured product layer on the fine relief structure side (unevenness forming surface side) is the average fluorine concentration (Eb) in the resin cured product layer. It is preferable to provide a concentration gradient from the surface layer on the film substrate side to the surface layer on the unevenness forming surface side. Thereby, the mold release property of the to-be-processed object from the fine concavo-convex structure of a resin cured material layer improves, maintaining the adhesiveness between a resin cured material layer and a film base material. That is, the releasability of the second film mold from the first film mold, the releasability of the third film mold from the second film mold, and the fineness from the second film mold. Improved mold release of structured products.

  In addition, as the concentration gradient of the cured resin layer, the fluorine element concentration (Es) of the cured resin layer on the fine uneven structure side (uneven formation surface side) is larger than the fluorine element concentration (Eb) in the cured resin layer. It may be anything as long as it is in a relatively large range. For example, the concentration gradient may change continuously and steplessly from the surface layer on the film substrate side of the resin cured product layer toward the surface layer on the fine concavo-convex structure side (the concavo-convex formation surface side). It may change in a stepwise manner. Further, in the thickness direction from the surface layer on the film substrate side of the cured resin layer to the fine relief structure side (irregularity forming surface side), the concentration gradient from the surface layer on the film substrate side to the center of the cured resin layer and The concentration gradient from the central part of the cured resin layer to the surface layer on the fine concavo-convex structure side (unevenness forming surface side) may be the same or may have a different concentration gradient.

  In this invention, the value calculated | required by the XPS method mentioned later is employ | adopted for the fluorine element concentration (Es) of the surface layer of a resin cured material layer. In the present invention, the fluorine element concentration (Es) is a measured value at a depth of several nm, which is the X-ray penetration length in the XPS method.

  On the other hand, in this specification, the average fluorine element concentration (Eb) in the cured resin layer is a value calculated from the charged amount, a value obtained by cutting the cured resin surface layer in advance to expose the inner surface, and a gas chromatograph. A value analyzed from a mass spectrometer (GC / MS) or a value analyzed from an ion chromatograph analysis is adopted. That is, it means the fluorine element concentration contained in the entire cured resin layer. For example, a section of a film-shaped mold composed of a cured product of a photopolymerizable mixture formed into a film, with the resin portion physically peeled off, is decomposed by a flask combustion method, followed by ion chromatography analysis. By applying, the average fluorine element concentration (Eb) in the photocurable resin can be identified.

  As the photocurable resin, for example, various acrylate compounds and methacrylate compounds that can be polymerized by a photopolymerization initiator, epoxy compounds, isocyanate compounds, thiol compounds, silicone compounds, and the like can be used. Among these, acrylate compounds, methacrylate compounds, epoxy compounds, and silicone compounds are preferably used, and acrylate compounds and methacrylate compounds are more preferably used. These compounds may be used alone or in combination of a plurality of types such as a combination of an epoxy compound and an acrylate compound.

  As acrylate compounds and methacrylate compounds, aromatic (meth) acrylates such as (meth) acrylic acid, phenoxyethyl acrylate, and benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3- Hydrocarbon-based (meth) such as butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, and dipentaerythritol hexaacrylate Acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diety (Meth) acrylates containing etheric oxygen atoms, such as 2-glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, and tripropylene glycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Hydrocarbon (meth) acrylates containing functional groups such as propyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinylpyrrolidone, and dimethylaminoethyl methacrylate And silicone-based acrylates.

  Examples of the acrylate compound and the methacrylate compound include EO-modified glycerol tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, EO-modified trimethylolpropane tri (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipenta Lithritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, penta Erythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) Acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di ( (Meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meta) ) Acrylate, EO modified neopentyl glycol diacrylate, PO modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentylglycol Stearic acid modified pentaerythritol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly ( Propylene glycol-tetramethylene glycol) di (meth) acrylate, polypropylene glycol di (meth) acrylate, silicone di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyester (di) Acrylate, polyethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propylene Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, divinylethylene urea, divinylpropylene urea 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid Immer, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate , Ethyl (meth) acrylate, dipropylene glycol (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl ( (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropyle Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxy Polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, ECH modified phenoxy acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meta ) Acrylate, phenoxytetraethylene glycol ( Acrylate), phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, Examples include tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, and silicone-based acrylate compounds. Here, EO modification means ethylene oxide modification, ECH modification means epichlorohydrin modification, and PO modification means propylene oxide modification. These can be used alone or in combination of two or more. In addition, commercially available resins for nanoimprinting such as PAK series (manufactured by Toagosei Co., Ltd.), NIF series (manufactured by AGC Co., Ltd.), NIAC series (manufactured by Daicel Chemical Industries, Ltd.) and the like can be used. Among these, PAK-02 and NIAC-702 are particularly preferable from the viewpoint of application characteristics to a resin sheet and pattern transferability.

  Moreover, as a photocurable resin, the fluorine-containing compound by which the hydrogen in hydrocarbon was substituted by the fluorine among the said acrylate compound, a methacrylate compound, an epoxy compound, an isocyanate compound, and a silicone type compound can be used. By using the fluorine-containing compound, the surface free energy after curing is reduced, and the transferred product (first film mold) from the original plate (cylindrical mold 107 and first film mold 103) in the transfer process is reduced. 103 and the second film-like mold 203) are improved.

  The fluorine-containing (meth) acrylate preferably has a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain and a polymerizable group, and is a linear perfluoroalkylene group or a carbon atom-carbon atom. More preferred is a perfluorooxyalkylene group having an etheric oxygen atom inserted therein and having a trifluoromethyl group in the side chain. Further, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.

  The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. Moreover, the polyfluoroalkylene group may have a functional group.

The perfluoro (polyoxyalkylene) chain is a group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ O) units. It is preferably composed of one or more perfluoro (oxyalkylene) units selected from: (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, or (CF ₂ CF ₂ CF ₂ O). ) Units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units since the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent. The number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, because the release property and hardness of the fluoropolymer are high.

As the polymerizable group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an epoxy group, a dichitacene group, a cyano group, an isocyanate group, or a formula — (CH ₂ ) _a Si (M1) 3-b (M2) _b The hydrolyzable silyl group is preferable, and an acryloyl group or a methacryloyl group is more preferable. Here, M1 is a substituent which is converted into a hydroxyl group by a hydrolysis reaction. Examples of such a substituent include a halogen atom, an alkoxy group, and an acyloxy group. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable. As M1, an alkoxy group is preferable, and a methoxy group is more preferable. M2 is a monovalent hydrocarbon group. Examples of M2 include an alkyl group, an alkyl group substituted with one or more aryl groups, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group, and an alkyl group or an alkenyl group is preferable. When M2 is an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. When M2 is an alkenyl group, an alkenyl group having 2 to 4 carbon atoms is preferable, and a vinyl group or an allyl group is more preferable. a is an integer of 1 to 3, and 3 is preferable. b is 0 or an integer of 1 to 3, and 0 is preferable. Examples of the hydrolyzable silyl group include (CH ₃ O) ₃ SiCH ₂ —, (CH ₃ CH ₂ O) ₃ SiCH ₂ —, (CH ₃ O) ₃ Si (CH ₂ ) ₃ — or (CH ₃ CH ₂ O ) ₃ Si (CH ₂ ) ₃ — is preferred.

  The number of polymerizable groups is preferably an integer of 1 to 4 and more preferably an integer of 1 to 3 because of excellent polymerizability. When using 2 or more types of compounds, as for the average number of polymeric groups, 1-3 are preferable.

  If the fluorine-containing (meth) acrylate has a functional group, the adhesiveness with the film-like substrate is excellent. Examples of the functional group include a carboxyl group, a sulfonic acid group, a functional group having an ester bond, a functional group having an amide bond, a hydroxyl group, an amino group, a cyano group, a urethane group, an isocyanate group, and a functional group having an isocyanuric acid derivative. It is done. In particular, it preferably contains at least one functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative. The isocyanuric acid derivatives include those having an isocyanuric acid skeleton and a structure in which at least one hydrogen atom bonded to a nitrogen atom is substituted with another group. As the fluorine-containing (meth) acrylate, fluoro (meth) acrylate, fluorodiene, or the like can be used. Specific examples of the fluorine-containing (meth) acrylate include the following compounds.

The fluoro (meth) _{acrylate, CH 2 = CHCOO (CH 2} ) 2 (CF 2) 10 F, CH 2 = CHCOO (CH 2) 2 (CF 2) 8 F, CH 2 = CHCOO (CH 2) 2 ( CF ₂ ) ₆ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F, CH _{2 = C (CH 3) COO (} CH 2) 2 (CF 2) 6 F, CH 2 = CHCOOCH 2 (CF 2) 6 F, CH 2 = C (CH 3) COOCH 2 (CF 2) 6 F, CH 2 = CHCOOCH ₂ (CF ₂ ) ₇ F, CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₇ F, CH ₂ = CHCOOCH ₂ CF ₂ CF ₂ H, CH ₂ = CHCOOCH ₂ (CF _{2 CF 2) 2 H, CH 2} = CHCOOCH 2 (CF 2 CF 2) 4 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) H, CH 2 = C (CH 3) COOCH 2 (CF _{2 CF 2) 2 H, CH} 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 = CHCOOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = CHCOOCH 2 CF 2 O (CF _{2 CF 2 O) 3 CF 3} , CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = C (CH 3) COOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF _{3, CH 2 = CHCOOCH 2 CF} (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = CHCOOCH 2 CF (CF 3) O _{CF 2 CF (CF 3) O} ) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = _{C (CH 3) COOCH 2 CF} (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF _{3) 2, CH 2 = CFCOOCH} 2 CH (CH 2 OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = _{CFCOOCH 2 CH (OH) CH 2} (CF 2) 10 F, CH 2 = CHCOOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 OCOCH = CH 2, CH 2 = C (CH 3 _{COOCH 2 CH 2 (CF 2 CF} 2) 3 CH 2 CH 2 OCOC (CH 3) = CH 2, CH 2 = CHCOOCH 2 C y FCH 2 OCOCH = CH 2, CH 2 = C (CH 3) COOCH 2 C y Examples include fluoro (meth) acrylates such as FCH ₂ OCOC (CH ₃ ) ═CH ₂ (where C _y F represents perfluoro (1,4-cyclohexylene group)). ).

The _{fluorodiene, CF 2 = CFCF 2 CF =} CF 2, CF 2 = CFOCF 2 CF = CF 2, CF 2 = CFOCF 2 CF 2 CF = CF 2, CF 2 = CFOCF (CF 3) CF 2 CF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂ , CF ₂ = CFOCF ₂ OCF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF = CF ₂ , CF ₂ = CFCF ₂ C _{(OH) (CF 3) CH} 2 CH = CH 2, CF 2 = CFCF 2 C (OH) (CF 3) CH = CH 2, CF 2 = CFCF 2 C (CF 3) (OCH 2 OCH 3) CH 2 Fluorodienes such as CH═CH ₂ , CF ₂ ═CFCH ₂ C (C (CF ₃ ) ₂ OH) (CF ₃ ) CH ₂ CH═CH _2, etc. may be mentioned.

  The fluorine-containing (meth) acrylate is a fluorine-containing urethane (meth) acrylate represented by the following chemical formula (1) and / or a fluorine-containing (meth) acrylate represented by the following chemical formula (2). Since the surface free energy of the fine uneven structure (unevenness forming surface) of the cured resin layer can be further reduced, the adhesion between the cured resin layer and the film-like substrate is improved. Moreover, since the average fluorine element density | concentration (Eb) in a resin hardened | cured material layer can be reduced and the intensity | strength of a resin hardened | cured material layer can be maintained, since repeat transferability improves more, it is preferable.

（化学式（１）中、Ｒ１は、下記化学式（３）を表し、Ｒ２は、下記化学式（４）を表す。）

(In the chemical formula (1), R1 represents the following chemical formula (3), and R2 represents the following chemical formula (4).)

（化学式（３）中、ｎは、１以上６以下の整数である。）

(In chemical formula (3), n is an integer of 1-6.)

（化学式（４）中、Ｒは、Ｈ又はＣＨ３である。）

(In the chemical formula (4), R is H or CH3.)

  As a fluorine-containing (meth) acrylate, 1 type may be used independently and 2 or more types may be used together. Further, it can be used in combination with surface modifiers such as abrasion resistance, scratch resistance, fingerprint adhesion prevention, antifouling property, leveling property and water / oil repellency. For example, “Fuategent (registered trademark)” manufactured by Neos (for example, M series: Aftergent (registered trademark) 251, Aftergent (registered trademark) 215 M, Aftergent (registered trademark) 250, FTX-245M, FTX-290M S series: FTX-207S, FTX-211S, FTX-220S, FTX-230S; F series: FTX-209F, FTX-213F, Footgent (registered trademark) 222F, FTX-233F, Footent (registered trademark) 245F G series: Footage (registered trademark) 208G, FTX-218G, FTX-230G, FTS-240G; Oligomer series: Footent (registered trademark) 730FM, Footent (registered trademark) 730LM; series "Fagent (registered trademark) 710FL, FTX-710HL, etc.", DIC "MegaFac (registered trademark)" (for example, F-114, F-410, F-493, F-494, F-443, F-) 444, F-445, F-470, F-471, F-474, F-475, F-477, F-479, F-480SF, F-482, F-483, F-487, F-172D, F-178K, F-178RM, MCF-350SF, etc.), “OPTOOL (registered trademark)” (for example, DSX, DAC, AES), “F-Tone (registered trademark)” (for example, AT-100), manufactured by Daikin "Zeffle (registered trademark)" (for example, GH-701), "Unidyne (registered trademark)", "Daifree (registered trademark)", "Optoace (registered trademark)", Sumitomo 3E Company Ltd., "Novec (registered trademark) EGC-1720", Fluoro Technology Co., Ltd. "Furorosafu (registered trademark)" and the like.

  As the fluorine-containing (meth) acrylate, the weight average molecular weight Mw is preferably 50 to 50,000, and from the viewpoint of compatibility, the weight average molecular weight Mw is preferably 50 to 5000, and the weight average molecular weight Mw is 100 to 5000. It is more preferable that When using a high molecular weight having low compatibility, a diluting solvent may be used. As a dilution solvent, the solvent whose boiling point of a single solvent is 40 to 180 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 140 degreeC is further more preferable. Two or more kinds of diluents may be used.

  The photocurable resin preferably contains a photopolymerization initiator in order to improve photosensitivity. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, and a photobase generator. The photopolymerization initiator can be selected in consideration of the light source wavelength to be used, the substrate (transparent sheet), various physical properties, and the like. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2- Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate, thioxanthone, 2 -Methylthioxanthone, 2-isopropylthioxanthone, diethylthioxyl Benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4 -(Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, bis (2,4,6- Limethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like are preferable. These may be used alone or in combination as a mixture. Examples of commercially available initiators include “IRGACURE®” manufactured by Ciba (for example, IRGACURE® 651, 184, 1173, 2959, 127, 907, 369, 379, 379EG, 819, 819DW, 784, OXE01, OXE02, 500), “DAROCUR (registered trademark)” (for example, DAROCUR (registered trademark) 1173, MBF), “LUCIRIN (registered trademark) TPO”, and the like.

  As a photocurable resin, what contains a sensitizer for a photosensitivity improvement is preferable. Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethyla) Nobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine , Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylamino Isoamyl benzoate, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) Examples include benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. Moreover, a sensitizer may be used individually by 1 type and may use multiple types as a mixture.

  The viscosity of the photocurable resin can be adjusted by adding a solvent. As the solvent, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide Pyridine, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate, methanol, ethanol, isopropyl alcohol and the like are preferable. These solvents may be used alone or in combination of two or more. Among these solvents, N-vinyl-2-pyrrolidone, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, and isopropyl alcohol are preferable. These solvents can be appropriately added according to the coating method, coating film thickness and viscosity of the photocurable resin, and are not limited. For example, the solvent is added to 100 parts by weight of the curable resin. 1 part by weight to 10000 parts by weight can be added.

  The viscosity of the photocurable resin can be appropriately adjusted depending on the monomers and solvents such as acrylate and methacrylate used. In order to transfer a fine uneven structure of submicron or less by photocuring, 1000 mPa · sec or less is preferable, and in order to improve transfer followability and throughput, 200 mPa · sec or less is more preferable. Furthermore, if it is 50 mPa · sec or less, a fine uneven structure of submicron or less can be transferred instantaneously.

  The photocurable resin can be cured by, for example, photocuring, thermosetting, electron beam curing, and microwave. Among these, it is preferable to use photocuring. After the photocurable resin is applied to the film substrate by the above application method, the photocurable resin is irradiated with light with an arbitrary amount of light at a predetermined wavelength, thereby promoting the curing reaction of the photocurable resin.

(Applying means)
Examples of the coating method of the photocurable resin onto the film-like substrate by the coating means 105 and 205 include a coating method using a known coating coater or impregnation coating coater. Specific examples include coating methods using a gravure coater, micro gravure coater, blade coater, wire bar coater, air knife coater, dip coater, comma knife coater, spray coater, curtain coater, spin coater, laminator and the like. These coating methods may use one type of coating method as needed, or may be used in combination of two or more types of coating methods. In addition, these coating methods are preferably applied in a continuous manner from the viewpoint of productivity. A continuous coating method using a dip coater, comma knife coater, gravure coater or laminator is particularly preferred.

(light source)
The light sources (light irradiating means) 109 and 210 used for light irradiation to the photocurable resin are not particularly limited, and various light sources can be used depending on the application and equipment. For example, a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a metal halide lamp, an excimer lamp, an LED lamp, a xenon pulse ultraviolet lamp, or the like can be used. Further, photocurable resins can amount exposed to ultraviolet rays or visible light having a wavelength 200nm~500nm is cured by irradiation so as to ^{100mJ / cm 2 ~2000mJ / cm 2} . Further, from the viewpoint of preventing the inhibition of the photocuring reaction due to oxygen, it is desirable to irradiate light with a low oxygen concentration during light irradiation.

(Cylindrical mold)
A cylindrical mold 107 is preferably used for the original plate used for the production of the first film mold 103 from the viewpoint of continuous productivity and yield. The cylindrical mold 107 is more preferably seamless. If there is a seam, the final product with a fine relief structure will be cut off where there is no fine relief structure corresponding to the seam, which will not only reduce the yield, but will add extra work for continuous production. Sexuality also deteriorates.

  As the cylindrical mold 107, a cylindrical mold having a fine uneven structure on the outer peripheral surface is used. The fine uneven structure corresponds to the shape of the fine uneven structure of the product with the fine uneven structure to be manufactured.

  The fine concavo-convex structure of the cylindrical mold 107 is formed by a processing method such as a laser cutting method, an electron beam drawing method, a photolithography method, a direct drawing lithography method using a semiconductor laser, an interference exposure method, an electroforming method, or an anodizing method. It can be directly formed on the outer peripheral surface of a cylindrical substrate. Among these, from the viewpoint of obtaining a cylindrical mold that is seamless in the fine concavo-convex structure, a photolithography method, a direct drawing lithography method using a semiconductor laser, an interference exposure method, an electroforming method, and an anodic oxidation method are preferable. A direct drawing lithography method, an interference exposure method, and an anodic oxidation method are more preferable.

  Further, as the cylindrical mold 107, the fine structure formed on the surface of the flat substrate by the above processing method is transferred to a resin material (film), and this film is bonded to the outer peripheral surface of the cylindrical mold with high positional accuracy. May be used. Moreover, the fine structure formed on the surface of the flat substrate by the above processing method may be transferred to a thin film such as nickel by electroforming, and the thin film wound around a roller may be used.

  As the material of the cylindrical mold 107, it is desirable to use a material that can easily form a fine uneven structure and has excellent durability. From such a viewpoint, a glass roll, a quartz glass roll, a nickel electroformed roll, a chromium electroformed roll, an aluminum roll, or a SUS roll (stainless steel roll) is preferable.

  As the base material for the nickel electroforming roll and the chromium electroforming roll, a conductive material having conductivity can be used. As the conductive material, for example, materials such as iron, carbon steel, chrome steel, cemented carbide, steel for mold (for example, maraging steel), stainless steel, aluminum alloy and the like are preferably used.

  It is desirable to perform a mold release process on the surface of the cylindrical mold 107. By performing the mold release treatment, the surface free energy of the cylindrical mold 107 can be reduced. Therefore, even when continuously transferred to a photo-curing resin, good releasability and pattern shape of a fine uneven structure Can be held. Moreover, since the mold release property of the cylindrical metal mold | die 107 is reflected from the 1st film mold 103 to the 2nd film mold 203 replicated, it is preferable to perform a mold release process. In the production of the first film mold 103, the fluorine component is strongly segregated by contacting the photocurable resin with the surface of the cylindrical mold 107 having low surface free energy achieved by the opposing mold release treatment. Is done. When the second film-shaped mold 203 is duplicated from the first film-shaped mold 103, the process proceeds by the same mechanism. Therefore, depending on the surface condition of the mold in the first first film-shaped mold manufacturing process, the post-process The releasability and transferability are controlled.

  A commercially available release agent and surface treatment agent can be used for the release treatment. Examples of commercially available release agents and surface treatment agents include OPTOOL (registered trademark) (manufactured by Daikin Chemical Industry), Durasurf (registered trademark) (manufactured by Daikin Chemical Industry), Novec (registered trademark) series (3M Company). Manufactured). Moreover, as a mold release agent and a surface treatment agent, a suitable mold release agent and a surface treatment agent can be selected suitably by the combination with the kind of material of the cylindrical metal mold | die 107, and the photocurable resin transcribe | transferred. .

  In order to improve the adhesion between the release agent and the surface treatment agent and the surface of the cylindrical mold, a metal film and an oxide film can be formed. Various known surface treatments such as UV ozone treatment, excimer treatment and corona treatment can be applied to the surface of the cylindrical mold. As a result, not only the adhesion between the surface of the cylindrical mold and the release agent, but also the durability is improved.

  A rubber roll is preferably used for the pressing unit 108, the bonding unit 207, and the release unit 211. Various commercially available materials can be used as the material for the rubber roll, such as nitrile butadiene rubber, ethylene propylene rubber, urethane rubber, silicon rubber, fluorine rubber, butadiene rubber, styrene butadiene rubber, acrylic rubber, ethylene vinyl acetate copolymer. Various types such as coalescence and natural rubber can be used. Nitrile butadiene rubber, ethylene propylene rubber, urethane rubber, silicon rubber, and fluorine rubber are preferred from the viewpoints of wear resistance, chemical resistance, and weather resistance. The rubber roll to be used is preferably black from the viewpoint of suppressing reflection of the UV light source.

  The hardness of the rubber roll is preferably a Shore hardness of 50 degrees or less, and more preferably a Shore hardness of 30 degrees or less. If the shore hardness is 50 degrees or less, the transfer of the fine structure is good, and if pressed at a low pressure, the spread of the photocurable resin can be suppressed, and if the shore hardness is 30 degrees or less, the pressure is 0.1 MPa. However, it will not spread if it is a photocurable resin having a viscosity of 40 cP or more. The thickness of the rubber layer of the rubber roll is preferably 10 mm or more. If it is 10 mm or more, it is not influenced by the rigid body used for the core material of the rubber roll.

(Preparation of nth film mold)
In the film mold manufacturing method according to the present embodiment described above, the second film mold 203 is formed using the first film mold 103 produced by transferring the fine concavo-convex structure from the cylindrical mold 107 as an original plate. The case of duplicating was explained. However, it is also possible to further replicate the third film mold using the second film mold 203 as an original plate. That is, the present invention can be applied from the (n-1) th (n is an integer of 2 or more) film-shaped mold to the n-th film-shaped mold manufacturing method.

  FIG. 6 is an explanatory view showing a method of manufacturing the nth film mold according to the present embodiment. As shown in FIG. 6, a first film mold M-1 is prepared using a cylindrical mold M-0 as an original plate, and a second film mold M1 is formed using the first film mold M-1 as an original plate. -2 can be duplicated. Further, the third film mold M-3 can be duplicated using the second film mold M-2 as an original plate. Similarly, the n-th film mold M-n can be duplicated using the (n-1) -th film mold M- (n-1) as an original plate.

  Any of the 2nd to n-th film molds M-2 to M-n manufactured as described above can be used for mass-producing the product P with a fine concavo-convex structure using this as an original plate.

  Examples performed to confirm the effects of the present invention will be described below. “Es / Eb” used in the description of Examples and Comparative Examples refers to the surface fluorine element concentration (Es) measured by the XPS method and the average fluorine element concentration (resin) of a resin mold having a fine concavo-convex structure on the surface. It means the ratio of Eb).

  Moreover, the surface fluorine element density | concentration of the resin mold was measured by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy: XPS). Since the penetration length of X-rays into the sample surface in XPS is as shallow as several nm, the measured value of XPS was adopted as the fluorine element concentration (Es) on the resin mold surface in the present invention. The resin mold was cut out as a small piece of about 2 mm square and covered with a 1 mm × 2 mm slot type mask and subjected to XPS measurement under the following conditions.

XPS measurement conditions Equipment used: Thermo Fisher ESCALAB250
Excitation source; mono. AlKα 15kV × 10mA
Analysis size: approx. 1 mm (shape is oval)
Capture area Survey scan; 0 to 1, 100 eV
Narrow scan; F 1s, C 1s, O 1s, N 1s
Pass energy
Survey scan; 100 eV
Narrow scan; 20 eV

  On the other hand, in order to measure the average fluorine element concentration (Eb) in the resin constituting the resin mold, the section physically cut so that the inside of the resin is exposed is obtained by XPS in the same manner as the surface fluorine concentration analysis. The average fluorine element concentration (Eb) was measured.

(First film mold production process)
(A) Cylindrical mold preparation A quartz glass roll was used as the base of the cylindrical mold, and a fine concavo-convex structure was formed on the surface of the quartz glass roll by a direct drawing lithography method using a semiconductor laser. A Cr film is laminated on the surface of the quartz glass roll, then OPTOOL (registered trademark) HD-1100Z (manufactured by Daikin Chemical Industries) is applied, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours. Immobilized. Then, it wash | cleaned 3 times with OPTOOL (trademark) HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented.

(B) Photocurable resin OPTOOL (registered trademark) DAC HP (manufactured by Daikin Industries, Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M350), Irgacure (registered trademark) 184 (manufactured by Ciba) and Irgacure (registered trademark) 369 (manufactured by Ciba) was mixed to prepare a photocurable resin. 10-20 parts by mass of OPTOOL (registered trademark) DAC HP (manufactured by Daikin Industries, Ltd.) was added to 100 parts by mass of trimethylolpropane triacrylate (M350, manufactured by Toagosei Co., Ltd.). In the film-shaped mold duplicating step for producing the second film-shaped mold from the first film-shaped mold described later, the same resin as that used for producing the first film-shaped mold is used, and the second A film-shaped mold was prepared.

PET film: A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm), by microgravure coating (manufactured by Yanai Seiki Co., Ltd.), the first coating width (W1) is 270 mm and the coating film thickness is 2 μm. A photocurable resin was applied so as to be. Next, the PET film coated with the photocurable resin was pressed against the cylindrical mold with a nip roll (ethylene propylene rubber, hardness 30, black, t10 mm, 0.1 MPa), and the temperature was 22 ° C. and the humidity was 40%. Then, UV curing is performed using UV exposure equipment (H bulb) manufactured by Fusion UV Systems Japan, Inc. so that the integrated exposure under the lamp center is 1200 mJ / cm ^2, and photocuring is continuously performed. As a result, a first film-like mold having a fine concavo-convex structure transferred onto the surface was obtained. The shape of the fine concavo-convex structure of the first film mold was confirmed by observation with a scanning electron microscope. As a result, the adjacent distance between the convex portions was 700 nm and the convex portion height was 650 nm.

  The surface fluorine element concentration (Es) near the center in the width direction of the obtained first film mold was 35 atom%, and the fluorine element concentration (Eb) in the resin was 9 atom%. Therefore, the ratio (Es / Eb) was 3.89.

(Second film-like mold replication process)
PET film: A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) The same adhesive as the resin used when the first film mold was produced by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) The photocurable resin was applied so that the application width was 250 mm and the application film thickness was 2 μm. Next, a PET film coated with a photocurable resin was applied to a nip roll (ethylene propylene rubber, hardness 30, black) on the formation surface of the fine concavo-convex structure of the first film mold obtained by direct transfer from the cylindrical mold. , T10 mm, 0.1 MPa), manufactured by Fusion UV Systems Japan Co., Ltd. so that the total exposure amount under the center of the lamp is 1200 mJ / cm ^{2 at} a temperature of 22 ° C. and a humidity of 40%. After UV irradiation using a UV exposure device (H bulb), photocuring is carried out continuously, and after the fine concavo-convex structure is transferred to the surface and peeled off, it has the same fine concavo-convex structure as a cylindrical mold. A second film mold was obtained. At this time, the conveyance distance of the 1st film mold from the bonding point by a nip roll to a mold release point and the conveyance distance of the 2nd film mold were both 0.32 m, and were the same. Moreover, as a result of confirming the shape of the fine concavo-convex structure of the second film-shaped mold by observation with a scanning electron microscope, the opening width of the recesses was φ600 nm, the adjacent distance between the recesses was 700 nm, and the recess height was 650 nm. In the production of the second film-shaped mold, there was no defect that embraced bubbles.

(Third film mold production process)
In the same manner as in the second film-shaped mold duplication step, the third film-shaped mold was manufactured such that the coating width of the third film-shaped mold was narrower than the coating width of the second film-shaped mold. A resin similar to the resin used in producing the second film mold was used to produce a third film mold. The shape of the fine concavo-convex structure of the obtained third film-shaped mold was confirmed by observation with a scanning electron microscope. As a result, the opening width of the convex portions was φ600 nm, the adjacent distance between the convex portions was 700 nm, and the convex portion height was 650 nm. Met. In the production of the third film mold, there was no defect that embeds bubbles.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effects of the present invention are exhibited.

  The present invention can be applied to a film mold manufacturing method for forming a fine relief structure, and the obtained film mold includes, for example, production of an antireflection material, production of a resist mask, cell culture medium, It can be suitably applied to superhydrophobic processing and superhydrophilic processing.

DESCRIPTION OF SYMBOLS 1,103 1st film-shaped mold 11, 101 Mold base material 11a Surface 12 Resin hardened | cured material layer (photocurable resin layer)
12a Fine concavo-convex structure 100, 200 Manufacturing apparatus 101 Mold substrate 104 Winding roll 107 Cylindrical mold 108 Pressing means 109, 210 Light source 201 Transferred substrate 202 First delivery roll (first delivery means)
203 2nd film-shaped mold 204 1st winding roll (1st winding means)
206 Second delivery roll (second delivery means)
207 Bonding means 207a, 207b Laminating roll 211 Mold releasing means 211a, 211b Peeling roll 212 Second winding roll (second winding means)
220 Sending means 230 Winding means

Claims (5)

A mold base material; and a cured resin layer provided on the surface of the mold base material, wherein the cured resin layer contains a fluorine-containing substance on the surface of the mold base material. The photocurable resin layer is formed by applying the photocurable resin layer to the fine concavo-convex structure of the original plate, and pressing the photocurable resin layer to the original plate. Preparing a (n-1) th film mold (n is an integer of 2 or more) formed by photocuring
A step of applying a photocurable resin having a viscosity of 50 mPa · sec or less to the surface of a film-like transferred substrate to form a transferred resin layer;
Bonding the transferred resin layer of the transferred substrate to the surface on which the inverted structure of the fine uneven structure of the cured resin layer is formed;
Photocuring the transferred resin layer by irradiating light in a state where the cured resin layer and the transferred resin layer are in contact with each other;
Releasing the (n-1) th film mold from the transferred resin layer to obtain an nth film mold,
The fine concavo-convex structure has a nano-sized pitch,
When the transport distance of the (n-1) th film mold from the bonding point to the release point is d1, and the transport distance of the nth film mold is d2, [(d2-d1) / ( The average distance between d1 and d2)] × 1000000 (ppm) is in the range of 0 ppm to 3000 ppm, and the transport distances d1 and d2 are 0.1 m to 1.5 m. Method for manufacturing a mold. The fluorine element concentration (Es) of the surface layer on which the fine concavo-convex structure of the cured resin layer of the (n-1) th film mold is formed is based on the average fluorine concentration (Eb) in the cured resin layer. The method for producing a film-shaped mold according to claim 1, wherein Wherein n is 2, and method for producing a film-like mold according to claim 1 or claim 2, wherein the precursor is a cylindrical mold. The method for producing a film-shaped mold according to claim 3 , wherein a release treatment is performed on the surface of the cylindrical mold. A step of applying a photocurable resin on the surface of a film-like transfer substrate to form a transfer resin layer, and the transfer substrate on the surface of the cured resin layer on which the fine concavo-convex structure is formed Instead of the step of pasting the transferred resin layer of
A step of applying a photocurable resin to the surface of the cured resin layer on which the fine concavo-convex structure is formed to form a transferred resin layer;
A step of bonding the transferred resin layer to the surface of the film-like transferred substrate;
The method for producing a film mold according to any one of claims 1 to 4 , wherein the film mold is provided.

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