JP6010481B2 - Method for producing film mold - Google Patents

Description

  The present invention relates to a method for producing a film 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 above-mentioned molds are made of silicon, glass, aluminum, or nickel made by electroforming made therefrom. 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. On the other hand, 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 cured resin layer is peeled from the raw fabric roll to obtain a film 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).

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

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 transfer resin described in Patent Document 7 contains a fluorine-based surfactant or a release agent in advance, and improves the releasability from the mold at the time of transfer, and increases the heat resistance of the microstructure after transfer. Has contributed. However, the use of this microstructure as a film mold has not been studied.

  The present invention has been made in view of the above-described problems, and an object thereof is to provide a method for producing a film mold using a photocurable resin containing a fluorine-containing substance and having excellent releasability. To do.

  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 the transfer of the fine 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 of 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 a surface of the mold substrate. On top, a photocurable resin containing a fluorine-containing substance is applied with a first coating width to form a photocurable resin layer, and the photocurable resin layer is bonded to the fine uneven structure of the original, The photocuring of the surface region formed by photocuring the photocurable resin layer while pressing the photocurable resin layer against an original plate , and the fine uneven structure of the resin cured product layer is formed. Fluorine element concentration (Es) in the surface portion in the resin application area where the curable resin was originally applied is the fluorine element concentration in the surface area in the extended area newly generated by the photocurable resin layer being spread by the original plate Fi of (Es) higher than the (n-1) A step of preparing a mold (n is an integer of 2 or more), and a photocurable resin is applied to the surface of the film-like transfer substrate with a second application width narrower than the first application width. Te forming the transferred resin layer, the cured resin layer and the fine concavo-convex structure Chi the caries surface region formed the resins applied in the region of the steps of laminating said the transfer resin layer And a step of photocuring the transferred resin layer while pressing the cured resin layer against the transferred resin layer to obtain an n-th film mold.

  With this configuration, the transferred resin layer is sufficiently segregated on the surface of the surface region where the fine uneven structure of the cured resin layer of the (n-1) th film mold is formed, and the surface Since the transferred resin layer is bonded in the resin coating region having a high fluorine concentration, the releasability of the transferred resin layer from the resin hard material layer is high, and transfer defects of the fine concavo-convex structure can be prevented.

  In the method for producing a film mold of the present invention, the original plate is a cylindrical mold.

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

  In the method for producing a film mold of the present invention, the original plate is an (n-2) th film mold.

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

The film-shaped mold of 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 containing a fluorine-containing substance is applied at a first coating width to form a photocurable resin layer, the photocurable resin layer is bonded to a fine concavo-convex structure of an original, and the original is transferred to the original A film-shaped mold formed by photocuring the photocurable resin layer while pressing the photocurable resin layer, wherein the width of the fine concavo-convex structure transferred to the surface of the cured resin layer is the first mold in most narrower than the coating width, and, of the surface area where the fine concavo-convex structure is formed of the cured resin layer, the fluorine element concentration of the surface portion of the photocurable resin originally applied resin application region ( Es), the photocurable resin layer is pressed by the original plate Gerare being higher than the fluorine element concentration of the surface portion (Es) in newly generated extended area Te.

  According to the present invention, the fluorine-containing substance is sufficiently segregated on the surface of the surface region where the fine uneven structure of the resin cured product layer of the (n-1) th film mold is formed. Because the transferred resin layer is bonded in the resin coating area where the surface fluorine concentration is high, the transferred resin layer is highly releasable from the hard resin layer and prevents transfer defects of the fine uneven structure. it can.

It is the cross-sectional schematic diagram and plane schematic diagram which show 1 process of the manufacturing method of the 1st film mold used for the manufacturing method of the film mold which concerns on this Embodiment. It is the cross-sectional schematic diagram and plane schematic diagram which show 1 process of the manufacturing method of the 1st film mold used for the manufacturing method of the film mold which concerns on this Embodiment. It is the cross-sectional schematic diagram and plane schematic diagram which show 1 process of the manufacturing method of the 1st film mold used for the manufacturing method of the film mold which concerns on this Embodiment. It is a section schematic diagram showing one process of a manufacturing method of a film mold concerning this embodiment. It is the schematic which shows the manufacturing apparatus used for the production process of the 1st film-shaped mold of the manufacturing method of the film-shaped mold which concerns on this Embodiment. It is the schematic which shows the manufacturing apparatus used for the duplication process of the 2nd film-shaped mold of the manufacturing method of the film-shaped mold which concerns on this Embodiment. It is explanatory drawing which shows the manufacturing method of the nth film mold which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows each process of manufacture of the antireflection material using the nth film-shaped mold obtained with the manufacturing method of the film-shaped mold which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows each process of preparation of the resist mask using the nth film-shaped mold obtained with the manufacturing method of the film-shaped mold which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows each process of the other example of resist mask preparation using the nth film-shaped mold obtained with the manufacturing method of the film-shaped 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 meaning.

  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. A film mold is used as the original plate. The film mold as the original plate is referred to as a first film mold. The manufactured film mold is referred to 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.

  1 to 2 are a schematic cross-sectional view and a schematic plan view showing respective steps of a first method for producing a film-shaped mold used in the method for producing a film-shaped mold according to the present embodiment.

  First, as shown in FIGS. 1A and 1B, a photocurable resin is applied to the surface of the mold base 11 to form a photocurable resin layer 12. The photocurable resin is applied in a substantially strip shape along the running direction (MD) of the mold base 11. A direction substantially orthogonal to the running direction (MD) of the mold base 11 is referred to as a width direction, and the length of the photocurable resin layer 12 along the width direction is referred to as a first coating width W1.

  In the present embodiment, the photocurable resin contains a fluorine-containing substance in order to improve the releasability.

  Next, a cylindrical mold (not shown) is pressed against the uncured photocurable resin layer 12 to closely contact the fine concavo-convex structure formed on the peripheral surface of the cylindrical mold, and then photocured. As shown in FIG. 2A, the cured resin layer 12 having the fine uneven structure transferred thereon is provided on the surface to obtain the first film-like mold 10.

  When the cylindrical mold was pressed against the photocurable resin layer 12, the photocurable resin layer 12 was spread in the width direction and transferred to the cured resin layer 13 as shown in FIGS. 1A and 1B. The width of the fine concavo-convex structure (hereinafter referred to as the first transfer width W2) is larger than the first application width W1. The surface of the cured resin layer 13 on which the fine concavo-convex structure 14 is formed (hereinafter referred to as the concavo-convex formation surface) is formed by spreading the resin-coated region 13a originally coated with the photo-curable resin and the photo-curable resin. It can be distinguished from the newly generated expansion area 13b.

  The inventor has found that the fluorine concentration on the surface is different between the resin-coated region 13a and the extended region 13b. That is, since the fluorine-containing substance contained in the photocurable resin layer 12 has a high affinity with an interface having a small surface free energy such as an air surface, the fluorine-containing substance becomes a photocurable resin as time passes. It moves to the air layer side of the layer 12 and segregates on the surface by coming into contact with the air layer.

  In the resin application region 13a of the photocurable resin layer 12, the fluorine-containing substance is applied between the photocurable resin applied to the surface of the mold substrate 11 and transferred and photocured. Since there is sufficient time to move to and contact the air layer, the fluorine-containing material is sufficiently segregated on the surface.

  On the other hand, in the extended region 13b of the photocurable resin layer 12, since the uncured photocurable resin is spread by the mold and is relatively short time until photocuring, the movement time of the fluorine-containing material There is not enough segregation on the surface.

  As will be described later, when the second film mold is manufactured, the cured resin layer of the second film mold is peeled off from the first film mold, but the fluorine-containing substance is sufficiently segregated on the surface. Since the resin-coated region 13a has high peelability due to the fluorine-containing material, the transfer property of the fine concavo-convex structure 14 is excellent. However, in the extended region 13b where the fluorine-containing material is not sufficiently segregated on the surface, the fine uneven structure 14 cannot be transferred because the peelability is not sufficiently improved by the fluorine-containing material.

  3 and 4 are a schematic cross-sectional view and a schematic plan view showing one step of the method for producing the film-shaped mold according to the present embodiment.

  As shown in FIG. 3A, a transferred resin layer 32 formed on the surface of a film substrate (hereinafter referred to as a transferred substrate) 31 for the second film-shaped mold from the first film-shaped mold 10. The fine concavo-convex structure 14 is transferred. At this time, the length in the width direction of the transfer resin layer 32, that is, the second application width W3 is set so as to be within the resin application region 13a of the cured resin layer 13 so that the transfer resin layer 32 is accommodated in the resin application region 13a. The transfer resin layer 32 is bonded to the resin application region 13a with a width smaller than the first application width W1. Thereafter, the photocurable resin constituting the transferred resin layer 32 is photocured while pressing, and the transferred resin layer 32 after photocuring is peeled off together with the transferred substrate 31, as shown in FIG. 2 film mold 30 is obtained. A fine concavo-convex structure 33 corresponding to the fine concavo-convex structure 14 of the first film mold 10 is transferred to the transferred resin layer 32 of the second film-shaped mold 30.

  As shown in FIG. 4, the width of the transferred resin layer 32 after the fine concavo-convex structure is transferred and cured by pressing while pressing is referred to as a second transfer width W4.

  The transferred resin layer 32 is formed by applying a photocurable resin containing a fluorine-containing substance.

  In the method for manufacturing a film-shaped mold according to the present embodiment as described above, the first film-shaped mold 10 provided with the cured resin layer 13 having a bias in the degree of segregation of the fluorine-containing substance is transferred. When the transferred resin layer 32 made of an uncured photocurable resin formed on the surface of the substrate 31 is bonded, if a part of the transferred resin layer 32 reaches the extended region 13b, the fluorine-containing substance is sufficient. Since the fluorine concentration is low, the peelable resin layer 32 after photocuring is poorly peelable from the cured resin layer 13 of the first film-like mold 10 and the fine concavo-convex structure cannot be transferred. .

  However, the second coating width W3 of the transferred resin layer 32 is made smaller than the first coating width W1 of the cured resin layer 13 of the first film mold 10, and the transferred resin layer 32 is resin-coated. By bonding within the region 13a, the fluorine-containing material is sufficiently segregated, and the transferred resin layer 32 can be bonded only to the cured resin layer 13 of the resin-coated region 13a having a high surface fluorine concentration. Transfer defects of the structure 14 can be prevented.

  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. 5 is a schematic view showing a manufacturing apparatus used in the first film-shaped mold manufacturing process of the film-shaped mold manufacturing method according to the present embodiment. A manufacturing apparatus 100 shown in FIG. 5 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 photocurable resin layer is formed by applying a photocurable resin on the light transmissive mold base 101 delivered from the original 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 are directly pressed by the nip rolls 108a and 108b as the pressing means 108. May be irradiated with light. Further, light may be irradiated in a state where the tension of the mold base 101 is controlled by unwinding and winding control and the photocurable resin layer and the cylindrical mold are pressure-bonded. In these cases, the pressing pressure and the tension can be appropriately adjusted depending on the transferability of the photocurable resin layer.

(Second film mold replication process)
FIG. 6 is a schematic view showing a manufacturing apparatus used in the second film-shaped mold duplication process of the film-shaped mold manufacturing method according to the present embodiment.

  The manufacturing apparatus 200 shown in FIG. 6 includes a first delivery roll 202 for delivering the transfer target substrate 201 and a first take-up roll 204 for winding the completed second film mold 203. . Between the first delivery roll 202 and the first take-up roll 204, the first film-like mold 103 is placed on the surface of the substrate 201 to be transferred in order from the upstream side to the downstream side in the transport direction MD. Application means 205 for applying a photocurable resin, a second delivery roll 206 for delivering the first film mold 103, and for bonding the first film mold 103 and the substrate 201 to be transferred. A bonding unit 207, a guide roll 208, a pressing unit 209 for bringing the first film mold 103 and the transferred substrate 201 into close contact, a light source 210 for irradiating light to the photocurable resin layer, and a guide A roll 211 and a second take-up roll 212 for taking up the first film mold 103 are provided.

  The bonding means 207 is composed of a pair of laminate rolls 207a and 207b.

  The pressing means 209 presses the first film mold 103 and the transferred substrate 201 against the rubber roll 209a on which the first film mold 103 and the transferred substrate 201 are conveyed on the outer peripheral surface thereof. The nip rolls 209b and 209c are configured.

  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, a photocurable resin may be applied on the unevenness forming surface of the cured resin layer of the first film mold 103.

  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.

  As described above, the second application width W3 of the photocurable resin applied on the transfer substrate 201 is smaller than the first application width W1 of the cured resin layer of the first film mold 103. .

  Next, the unevenness forming surface of the resin cured product layer of the first film mold 103 unwound from the second delivery roll 206 by the bonding means 207 is applied to the photocurable resin layer on the substrate 201 to be transferred. to paste together.

  At this time, the photo-curable resin layer on the transferred substrate 201 is pasted into the resin application region on the uneven surface of the cured resin 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.

  The first film mold 103 and the substrate 201 to be transferred are supplied to the pressing unit 209 through the guide roll 208. In the pressing means 209, the uneven surface of the cured resin layer of the first film mold 103 is brought into close contact with the photocurable resin layer. In this state, the light curable resin is irradiated with light from the light source 210 to photocur the photocurable resin. The adhesion by the pressing means 209 can prevent uncured by oxygen.

  Thereafter, the first film-shaped mold 103 and the substrate to be transferred 201 are conveyed to the guide roll 211, where the substrate to be transferred has a cured resin layer formed on the surface from the first film-shaped mold 103. 201, that is, the second film mold 203 is peeled off. At this time, the inverted shape of the fine uneven structure of the first film mold 103 is transferred to 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.

  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 has a substantially light-transmitting property 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, and corona treatment in order to improve adhesion to 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 depending on the photocurable resin to be used, the film-like substrate is required to have good light 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 is formed of a photocurable resin. Photocurable resins are transferability, peelability from the original plate, adhesion to film-like substrates, viscosity, film-forming properties, photosensitivity, mechanical properties after curing, and peelability from the resin layer during resin mold preparation. Select with consideration.

  In the cured resin layer obtained by photocuring the photocurable resin layer, the fluorine element concentration (Es) in the surface portion of the concavo-convex formation surface on which the fine concavo-convex structure is formed is an average fluorine element in the photocurable resin layer. It is preferably higher than the concentration (Eb).

  According to this, since the fluorine element concentration (Es) on the unevenness forming surface side in the cured resin layer is relatively higher than the average fluorine element concentration (Eb) in the cured resin layer, for example, the second Releasability of the cured resin layer of the film-shaped mold from the first film-shaped mold, and from the second film-shaped mold in the case of producing a microstructured product developed from the second film-shaped mold. The releasability of products with fine structure 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 portion on the unevenness forming surface side of the cured resin layer is relative to the average fluorine concentration (Eb) in the cured resin layer. In other words, it is preferable to provide a concentration gradient from the surface portion on the film base side toward the surface portion 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.

  The concentration gradient of the cured resin layer is a range in which the fluorine element concentration (Es) of the cured resin layer on the unevenness forming surface side is relatively larger than the fluorine element concentration (Eb) in the cured resin layer. If it becomes, what kind of thing may be sufficient. For example, the concentration gradient may be continuously stepless from the surface portion on the film base side of the cured resin layer to the surface portion on the unevenness forming surface side, stepwise in a stepwise manner. It may change to. Further, in the thickness direction from the surface portion of the cured resin layer on the film substrate side to the unevenness forming surface side, a concentration gradient from the surface portion on the film-like substrate side to the central portion of the cured resin layer, and the cured resin product The concentration gradient from the central portion of the layer to the surface portion on the unevenness forming surface side may be the same or may have a different concentration gradient.

  In this invention, the value calculated | required by XPS method mentioned later is employ | adopted for the fluorine element density | concentration (Es) of the surface part 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.

The polymerizable group is represented by 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 ) aSi (M1) _3-b (M2) _b. A 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 CyFCH 2 OCOCH = CH 2, CH 2 = C (CH 3) COOCH 2 CyFCH 2 OCOC ( CH ₃₎ = fluoro, such as CH ₂ (meth) acrylate (where, CYF perfluoro (1,4-cyclohexylene-xylene 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 uneven | corrugated formation surface of a resin cured material layer can be made lower, the adhesiveness between a resin cured material layer and a film-form base material improves. 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ＣＨ_３である。）

(In the chemical formula (4), R is H or CH _3. )

  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, “Factent” manufactured by Neos Co., Ltd. (for example, M series: Futgent 251, Futgent 215M, Futgent 250, FTX-245M, FTX-290M; FTX-230S; F Series: FTX-209F, FTX-213F, Footage 222F, FTX-233F, Footage 245F; G Series: Footent 208G, FTX-218G, FTX-230G, FTS-240G; Oligomer Series: Footer Gent 730FM, tergent 730LM; tergent P series: tergent 710FL, FTX-710HL, etc.), DIC's "Megafuck" (for example, F-114, F-410, F-4) 3, 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-489, F-172D, F-178K, F-178RM, MCF-350SF, etc., Daikin's "OPTOOL (registered trademark)" (eg, DSX, DAC, AES), "Eftone (registered) Trademark) ”(for example, AT-100),“ Zeffle (registered trademark) ”(for example, GH-701),“ Unidyne (registered trademark) ”,“ Daifree (registered trademark) ”,“ Optoace (registered trademark) ” ”,“ Novec EGC-1720 ”manufactured by Sumitomo 3M Co.,“ Fluorosurf (registered trademark) ”manufactured by Fluoro Technology, Inc., 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, IRGACURE651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 1800, 784, OXE01, OXE02 ) And “DAROCUR” (for example, DAROCUR 1173, MBF, TPO, 4265).

  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 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 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 (manufactured by Daikin Chemical Industries), Durasurf (manufactured by Daikin Chemical Industries, Ltd.), Novec series (manufactured by 3M Corporation), and the like. Moreover, as a mold release agent and a surface treatment material, a suitable mold release agent and a surface treatment agent can be selected suitably by the combination with the material type of the cylindrical metal mold | die 107, and the photocurable resin transcribe | transferred. .

(Relationship between coating width and transfer width and transfer failure)
In the method for manufacturing a film mold according to the present embodiment, the first application width W1 refers to the width when the photocurable resin is applied to the mold substrate 101 from the application means 105. The first application width W1 is necessarily narrower than the width of the mold base 101.

  The fluorine atom-containing substance in the photocurable resin applied with the first application width W1 from the application means 105 is segregated on the surface by being in contact with the air layer. This is because the movement of the fluorine atom-containing substance to the air layer side having a small surface free energy is more energetically stable than existing in the photocurable resin. In order to enhance the mobility of the fluorine atom-containing substance, the photocurable resin after coating can be subjected to heat treatment.

  The first transfer width W2 means that the fine concavo-convex structure is transferred by the cylindrical mold 107 and the pressing means 108 to the photocurable resin applied on the mold base 101 with the first application width W1. Refers to the width. The photocurable resin before photocuring is pushed and spread along the width direction of the mold base 101 by the pressing means 108, and the first transfer width W2 is necessarily larger than the first coating width W1.

  The pressing means 108 is necessary for transferring the fine concavo-convex structure. The first transfer width W2 can be appropriately adjusted depending on the tension of the mold base 101, the type of the film base, or the viscosity of the photocurable resin.

  In order to prevent the photocurable resin from wrapping around the back surface of the mold base 101 by the pressing means 108, the first transfer width W2 is preferably smaller than the width of the mold base 101.

  Further, it is preferable that the pressing by the pressing unit 108 is as weak as possible. This is because the first transfer width W2 needs to be close to the first coating width W1 in order to increase the production area of the second film mold 203 that follows.

  The present inventor has found that the difference area between the first coating width W1 and the first transfer width W2, that is, the above-described extended region 13b (see FIGS. 2A and 2B) has the fine uneven structure transferred thereto. The surface fluorine concentration was found to be lower than that of the first application width W1 area. This is because the fluorine-containing material is sufficiently segregated when the photocurable resin applied with the first application width W1 comes into contact with the air layer, but in the difference area, the photocurable resin is pressed by the pressing means 108. Therefore, it is not an area that has been in contact with the air layer in advance, indicating that fluorine segregation is not sufficient.

  Since the fluorine-containing substance has high affinity with an interface having a small surface free energy such as an air surface or a release-treated cylindrical mold, the fluorine-containing substance moves to the air surface or the cylindrical mold 107 side. However, in the difference area where the photo-curable resin is spread and kneaded, the moving time is insufficient and segregation does not occur sufficiently. Although it is possible to promote fluorine segregation in the difference area by reducing the linear velocity of the mold base 101, this does not improve the throughput. The difference area where the fluorine atom-containing substance is not sufficiently segregated has a low surface fluorine concentration, and the subsequent second film mold 203 cannot be produced. Therefore, the second transfer width W4 of the second film mold 203 depends on the first application width W1 and needs to be narrower than the first application width W1.

  The second coating width W3 according to the present embodiment refers to a width obtained by coating a photocurable resin from the coating unit 205 onto the substrate 201 to be transferred. Therefore, the second coating width W3 is necessarily narrower than the width of the transfer target substrate 201. The fluorine-atom-containing substance in the photocurable resin applied with the second application width W3 from the application means 205 is segregated on the surface in the same manner as in the production of the first film mold 103 by contacting the air layer. .

  The second transfer width W4 according to the present invention refers to a fine concavo-convex structure formed by pressing means 209 from the first film-like mold 103 onto a photo-curable resin applied with a second application width W3 on the substrate 201 to be transferred. Refers to the width to which is transferred.

  Unlike the production of the first film-like mold 103, since the film-to-film transfer bonding, when the pressing means 209 is an elastic rubber roll, the photo-curing resin before photo-curing is largely pushed and spread. There may not be. This is because when the first film-shaped mold 103 is manufactured, the cylindrical mold 107 is a rigid body, so that the pressed photo-curing resin before photo-curing has only escape sides on the mold base 101. , Spread in the width direction. On the other hand, when duplicating the second film-shaped mold 203, unless the roll constituting the pressing means 209 is a rigid body, the pressure due to pressing is absorbed, so that the photocurable resin does not spread. That is, when the second film mold 203 is replicated, the second coating width W3 and the second transfer width W4 may be substantially the same.

  The pressing means 209 is necessary for transferring the fine uneven structure. The second transfer width W4 can be appropriately adjusted according to the tension of the substrate 201 to be transferred, the type of the film substrate, or the viscosity of the photocurable resin.

  As described above, the difference area between the first coating width W1 and the first transfer width W2 in which the fluorine atom-containing substance is not sufficiently segregated has a low surface fluorine concentration, and the second film mold 203 thereafter. Cannot be duplicated. Therefore, the second transfer width W4 of the second film mold 203 needs to be narrower than the first application width W1. In the differential area where the fluorine atom-containing substance of the first film mold 103 is not sufficiently segregated, the affinity of the photocurable resin after application in the replication of the second film mold 203 with the fluorine atom-containing substance is It is considered that a fluorine atom-containing substance segregated by contact with the air layer is dispersed in the resin. Since the difference area between the first coating width W1 and the first transfer width W2 has a low surface fluorine concentration, the releasability from the second film mold 203 is poor, and it may be impossible to transfer.

  When the photocurable resin is spread by the pressing means 209 and the second transfer width W4 becomes larger than the first application width W1, the difference area becomes a transfer defect. For this reason, it is preferable that the pressing by the pressing unit 209 at the time of duplicating the second film mold 203 is as weak as possible when the first film mold 103 is manufactured. The pressing means 209 is preferably a rubber roll rather than a rigid body such as a metal roll.

  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 method for producing the n-th film-shaped mold.

  FIG. 7 is an explanatory view showing a method of manufacturing the nth film mold according to the present embodiment.

  As shown in FIG. 7, 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.

  That is, the (n-1) th film mold M- (n-1) used for duplicating the nth film mold M-n is the previous (n-2) film. The mold M- (n-2) (not shown) was produced as an original plate.

  Thus, in the transfer of the fine concavo-convex structure from the (n-1) th film mold M- (n-1) as the original plate to the nth film mold Mn, as described above, n-1) film-like mold M- (n-1) second application at the time of duplication of the n-th film-like mold M-n than the first application width W1 of the photocurable resin at the time of production. The photocurable resin layer formed on the substrate to be transferred for the nth film mold M-n with the width W3 being reduced is the resin cured product of the (n-1) th film mold. It is the unevenness forming surface of the layer and is bonded to the resin application region 13a. As a result, the fluorine-containing substance of the (n-1) th film mold is sufficiently segregated, and the nth film mold M- is applied only to the cured resin layer 13 in the resin coating region 13a having a high fluorine concentration on the surface. The photocurable resin layer of n can be bonded, and the transfer defect of a fine concavo-convex structure can be prevented.

  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.

(Application example of nth film mold)
The nth film mold obtained by the method for manufacturing a film mold according to the present embodiment described above includes, for example, the manufacture of an antireflection material, the production of a resist mask, a cell culture medium, a super-water-repellent process, It can be applied to hydrophilic processing and is useful. Hereinafter, (1) manufacture of an antireflection material and (2) application examples to manufacture of a resist mask will be described.

(1) Manufacture of antireflection material A material having a periodic fine concavo-convex structure including a pillar shape, a cone shape, a pyramid shape, and a cone shape can be used as an antireflection film having a moth-eye structure having an antireflection effect. Here, the moth-eye structure refers to a structure in which submicron-order pyramidal concavo-convex structures are arranged in a two-dimensional pattern such as an eyelet. In such a fine structure, a nano-order fine concavo-convex structure formed on the surface induces a smooth curvature gradient, and no reflection caused by a difference in refractive index at the interface occurs. Therefore, it is suitable as an antireflection film. It can be used.

  FIG. 8 is a schematic cross-sectional view showing each step of manufacturing an antireflection material using the nth film mold obtained by the film mold manufacturing method according to the present embodiment.

  As shown in FIG. 8A, an nth film mold 801 is prepared. The n-th film-like mold 801 is composed of a film-like substrate 802 and a cured resin layer 803 having a fine uneven structure provided on the surface of the film-like substrate 802.

  Next, as shown in FIG. 8B, a resin 804 is applied to the fine uneven structure of the cured resin layer 803 of the nth film mold 801. At this time, it may be a molten resin or a solution. Further, the resin 804 may be any of a thermoplastic resin, a thermosetting resin, or a photocurable resin.

  Thereafter, as shown in FIG. 8C, the base material 805 is laminated on the resin 804. Furthermore, by peeling the nth film mold 801 from the resin 804, an antireflection material 800 can be obtained as shown in FIG. 8D.

(2) Production of resist mask A resist mask can be produced on the surface of the substrate to be etched using the nth film mold obtained by the method for producing a film mold according to the present embodiment.

  FIG. 9 is a schematic cross-sectional view showing each step of producing a resist mask using the nth film mold obtained by the method for producing a film mold according to the present embodiment.

  As shown in FIG. 9A, an nth film mold 901 is prepared. The n-th film-like mold 901 includes a film-like base material 902 and a cured resin layer 903 having a fine uneven structure provided on the surface of the film-like base material 902.

  Next, as shown in FIG. 9B, a resist material 904 is applied and embedded in the fine concavo-convex structure of the cured resin layer 903 of the nth film mold 901. The resist material 904 can be selected in accordance with the substrate to be used. When the resist material 904 is a resin, it may be a molten resin or a solution. The resin may be any of a thermoplastic resin, a thermosetting resin, a thermally decomposable resin, a photocurable resin, or a photodegradable resin.

  Thereafter, as shown in FIG. 9C, the substrate 905 is disposed on the cured resin layer 903, and the resist material 904 is bonded by some method. Furthermore, by releasing the n-th film mold 901, a resist mask 906 having an inverted structure of fine concavo-convex structure is formed on the surface of the substrate 905 as shown in FIG. 9D.

  FIG. 10 is a schematic cross-sectional view showing each step of another example of resist mask fabrication using the nth film mold obtained by the film mold manufacturing method according to the present embodiment.

  As shown in FIG. 10A, a resist material 1002 is applied on the surface of the substrate 1001. Next, as shown in FIG. 10B, the unevenness forming surface of the cured resin layer 903 of the nth film mold 901 is bonded to the resist material 1002 and pressed. Thereafter, the n-th film mold 901 is released, and a resist mask 1003 having an inverted structure of fine concavo-convex structure is formed on the surface of the substrate 1001 as shown in FIG. 10C.

  Note that an adhesive layer can be provided between the resist material 1002 and the substrate 1001, or a two-layer resist in which a resist material is stacked one more layer can be used.

  By etching the substrates 905 and 1001 using the resist masks 906 and 1003 manufactured as described above, a fine uneven structure can be formed on the substrates 905 and 1001.

  In the nth film molds 801 and 901 obtained by the method for manufacturing a film mold according to the present embodiment, the surface fluorine concentration on the unevenness forming surface side of the resin cured product layers 803 and 903 is high. The mold releasability from the resist materials 904 and 1002 is improved. In particular, when the n-th film-shaped molds 801 and 901 use a roll made of a hard material as the pressing means 209, the second application is similar to the second film-shaped mold 30 shown in FIGS. Since the surface fluorine concentration in the range of the width W3 (resin application region) is higher than the difference area (extended region) between the second application width W3 and the second transfer width W4, the resin 804, the resist material 904, Excellent releasability from 1002 and transferability.

  That is, the film-shaped mold according to the present embodiment includes a mold base material and a cured resin layer provided on the surface of the mold base material, and the cured resin layer includes the mold base material. A photocurable resin containing a fluorine-containing substance is applied on the surface of the substrate with a first coating width to form a photocurable resin layer, and the photocurable resin layer is bonded to the fine uneven structure of the original plate. , A film-like mold formed by photocuring the photocurable resin layer while pressing the photocurable resin layer against the original plate, the width of the fine concavo-convex structure transferred to the surface of the cured resin layer Is narrower than the first coating width.

  The original plate is preferably the (n-1) th film mold produced according to the method for producing a film mold according to the present embodiment. However, it may be a film mold manufactured by a method different from the present embodiment.

  In addition, when a roll made of a hard material is used for the pressing means 209 that presses the photocurable resin to the original plate, a difference area is likely to occur. Therefore, the improvement in releasability and transferability that are the effects of the present invention are remarkable. Demonstrated.

(Fine relief structure)
In the method for manufacturing a film-shaped mold according to the present embodiment, the fine concavo-convex structure is a pillar shape including a plurality of conical, pyramidal or elliptical cone-shaped convex portions, or a conical, pyramidal or elliptical cone shape. A hole shape or a line and space shape including a plurality of recesses. 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.

  The scale of the fine concavo-convex structure is not particularly specified because it depends on the application to be used, but it refers to tens of nanometers to tens of micrometers. The scale may be the size, diameter, depth, and pitch of one microstructure. A random structure can be one of the fine structures.

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.

[Example 1]
(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. Durasurf HD-1101Z (manufactured by Daikin Chemical Industries) was applied to the surface of the quartz glass roll, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours to be fixed. Then, it wash | cleaned 3 times by Durasurf HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented.

(B) Photocurable resin OPTOOL DAC HP (manufactured by Daikin Industries), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350), Irgacure 184 (manufactured by Ciba) and Irgacure 369 (manufactured by Ciba) are mixed, and light A curable resin was prepared. OPTOOL DAC HP (manufactured by Daikin Industries) was added in an amount of 10 to 20 parts by mass with respect 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 or third 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. The 2nd or 3rd film-like mold was produced.

PET film: A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yanai Seiki Co., Ltd.) so that the first coating width (W1) is 270 mm and the coating film thickness is 4 μm. A photo-curable resin was applied to the film. Next, a PET film coated with a photocurable resin is pressed against the cylindrical mold with a nip roll (0.1 MPa), and the integrated exposure amount under the center of the lamp is 22 ° C. and humidity 40% in the atmosphere. Ultraviolet rays were irradiated using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. so as to be 1200 mJ / cm ^2, and photocuring was carried out continuously. A first film-like mold (length 200 m, first transfer width (W2) 290 mm) was obtained. As a result of confirming the surface fine unevenness of the first film-shaped mold by observation with a scanning electron microscope, the adjacent distance between the protrusions was 460 nm, and the height of the protrusions was 460 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 second coating width (W3) was 250 mm and the coating film thickness was 4 μm. Next, a PET film coated with a photocurable resin was pressed with a nip roll (0.1 MPa) against the fine concavo-convex structure surface of the first film mold obtained by direct transfer from the cylindrical mold, Irradiate ultraviolet rays using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. so that the integrated exposure amount under the lamp center is 1200 mJ / cm ² at a temperature of 22 ° C. and a humidity of 40%. A second film-shaped mold (length: 180 m, second transfer width (W4) having a fine concavo-convex structure similar to a cylindrical mold, in which photocuring is continuously performed and the fine concavo-convex structure is transferred to the surface. ) 255 mm). The shape of the fine surface irregularities of the second film mold was confirmed by observation with a scanning electron microscope. As a result, the opening width of the recesses was φ230 nm, the adjacent distance between the recesses was 460 nm, and the recess height was 460 nm.

(Third film mold replication process)
In the same manner as the second film-shaped mold duplication step, the second film-shaped mold is used as an original plate, and the third coating width (W5) is made narrower than the second coating width (W3). A third film mold was produced. The shape of the surface fine irregularities of the obtained third film mold (length 170 m, third transfer width (W6) 240 mm) was confirmed by observation with a scanning electron microscope. As a result, the opening width of the convex portion was φ230 nm, The adjacent distance between the convex portions was 460 nm, and the convex portion height was 460 nm.

(Comparative example)
(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. Durasurf HD-1101Z (manufactured by Daikin Chemical Industries) was applied to the surface of the quartz glass roll, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours to be fixed. Then, it wash | cleaned 3 times by Durasurf HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented.

(B) Photocurable resin OPTOOL DAC HP (manufactured by Daikin Industries), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350), Irgacure 184 (manufactured by Ciba) and Irgacure 369 (manufactured by Ciba) are mixed, and light A curable resin was prepared. OPTOOL DAC HP (manufactured by Daikin Industries) was added in an amount of 10 to 20 parts by mass with respect 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.) so that the first coating width (W1) is 270 mm and the coating film thickness is 4 μm. A photo-curable resin was applied to the film. Next, a PET film coated with a photocurable resin is pressed against the cylindrical mold with a nip roll (0.1 MPa), and the integrated exposure amount under the center of the lamp is 22 ° C. and humidity 40% in the atmosphere. Ultraviolet rays were irradiated using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. so as to be 1200 mJ / cm ^2, and photocuring was carried out continuously. A first film-like mold (length 200 m, first transfer width (W2) 290 mm) was obtained. As a result of confirming the surface fine unevenness of the first film-shaped mold by observation with a scanning electron microscope, the adjacent distance between the protrusions was 460 nm, and the height of the protrusions was 460 nm.

  The surface fluorine element concentration (Es) in the vicinity of the first application area 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, 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 second coating width (W3) was 290 mm and the coating film thickness was 4 μm. Next, a PET film coated with a photocurable resin was pressed with a nip roll (0.1 MPa) against the fine concavo-convex structure surface of the first film mold obtained by direct transfer from the cylindrical mold, Irradiate ultraviolet rays using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. so that the integrated exposure amount under the lamp center is 1200 mJ / cm ² at a temperature of 22 ° C. and a humidity of 40%. Photocuring was carried out continuously.

  However, in the area of the difference between the second application width (W3) 290 mm and the first application width (W1) 270 mm, a peeling failure occurred.

  In addition, the surface fluorine element concentration in the area of the difference between the first transfer width (W2) and the second coating width (W3) of the first film mold that has caused the peeling failure during the production of the second film mold is , (Es) was 27 atom%, the fluorine element concentration (Eb) in the resin was 9 atom%, and the ratio, Es / Eb, was 3.00.

  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 10, 103 1st film-shaped mold 11, 101 Mold base material 12 Photocurable resin layer 13, 803, 903 Resin hardened material layer 14, 33 Fine uneven structure 30, 203 2nd film-shaped mold 31, 201 Transferred Substrate 32 Transferred resin layer 100, 200 Manufacturing apparatus 105, 205 Application means 107 Cylindrical mold 108, 209 Press means 109, 210 Light source 207 Bonding means

Claims (6)

A mold substrate and a cured resin layer provided on the surface of the mold substrate, and the cured resin layer is a photocuring containing a fluorine-containing substance on the surface of the mold substrate. A photocurable resin layer is applied to form a photocurable resin layer with a first coating width, the photocurable resin layer is bonded to the fine uneven structure of the original plate, and the photocurable resin layer is pressed onto the original plate. In the resin application region where the photocurable resin was originally applied among the surface regions formed by photocuring the photocurable resin layer and the fine uneven structure of the resin cured product layer being formed. The fluorine element concentration (Es) in the surface part is higher than the fluorine element concentration (Es) in the surface part in the expanded region newly generated by the photocurable resin layer being spread by the original plate (n−1). ) Film mold (n is an integer of 2 or more) And that process,
A step of applying a photocurable resin on the surface of a film-like transferred substrate with a second coating width narrower than the first coating width to form a transferred resin layer;
The cured resin layer and the fine concavo-convex structure formed the surface area sac Chi said resins applied in the region of the steps of laminating said the transfer resin layer,
A step of photocuring the transferred resin layer while pressing the cured resin layer against the transferred resin layer to obtain an nth film mold;
A method for producing a film-shaped mold, comprising:   2. The method for producing a film mold according to claim 1, wherein n is 2 and the original plate is a cylindrical mold.   3. The method for producing a film-shaped mold according to claim 2, wherein a release treatment is performed on the surface of the cylindrical mold.   The method for producing a film mold according to claim 1, wherein n is an integer of 3 or more, and the original plate is a (n-2) th film mold.   The fluorine element concentration (Es) in the surface portion of the cured resin layer of the (n-1) th film mold on the surface side where the fine uneven structure is formed is the average fluorine concentration in the cured resin layer. It is higher than (Eb), The manufacturing method of the film mold in any one of Claims 1-4 characterized by the above-mentioned. A mold substrate and a cured resin layer provided on the surface of the mold substrate, and the cured resin layer is a photocuring containing a fluorine-containing substance on the surface of the mold substrate. A photocurable resin layer is applied to form a photocurable resin layer with a first coating width, the photocurable resin layer is bonded to the fine uneven structure of the original plate, and the photocurable resin layer is pressed onto the original plate. while the photocurable resin layer to a film-like mold is formed by photocuring, the width of the transferred fine unevenness on the surface of the cured resin layer, rather narrower than the first coating width, And the fluorine element density | concentration (Es) of the surface part in the resin application area | region which originally applied the said photocurable resin among the surface area | regions in which the said fine concavo-convex structure of the said resin cured material layer was formed is the said photocurable property. Newly expanded area when the resin layer is pushed out by the original Filmy mold being greater than the fluorine element concentration of the surface portion (Es) in.

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