JP2013257373A - Dustproof film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly productive dustproof film manufacturing method in which dustproof films with antireflection performance and excellent transmittance over a wide region of wavelengths on which foreign objects hardly stick can be obtained and the area can be increased.SOLUTION: The method for manufacturing dustproof films comprises: a mold fabrication step of fabricating a reeled resin mold (12) provided with a base material (11) and a cured resin layer (14) having a fine uneven structure on the surface thereof; a resin cast fabrication step of fabricating a resin cast (15) provided with a cured resin layer (18) onto which the fine uneven structure of the reeled resin mold (12) is transferred; an uncured dustproof film material layer formation step of forming an uncured dustproof film material layer (19) on the cured resin layer (18); and a dustproof film peeling step of curing the uncured dustproof film material layer (19) to manufacture a dustproof film (20). The ratio of fluorine element concentration (Es) in the surface portion of the cured resin layer (18) to average fluorine element concentration (Eb) in the cured resin layer (18) is within a prescribed range.

Description

  The present invention relates to a method for manufacturing a dust-proof film used to prevent foreign matter from adhering to a surface, and in particular, IC (Integrated Circuit), LSI (Large Scale Integration), TFT LCD The present invention relates to a method of manufacturing a dustproof film suitably used for a photomask or a reticle used in a lithography process when manufacturing a semiconductor device such as a thin film transistor (Liquid Crystal Display).

  Conventionally, in the manufacture of semiconductor circuit patterns and the like, dust-proof films (dust-proofing means called pellicles) are arranged on both sides of a photomask or reticle to prevent foreign matter from adhering to the photomask or reticle. Yes. As a general structure of the dust-proof film, a transparent thin film such as a polymer or glass is attached to one side of a metal, ceramic, or polymer frame, and an adhesive layer for attaching to a mask on the opposite side. What provided (adhesive material) is mentioned. In the production of a semiconductor circuit pattern or the like, for example, a fluororesin having a thickness of 10 μm or less, nitrocellulose or A dust-proof film made of a transparent polymer film such as a cellulose derivative is stretched and bonded, and is attached to the other edge surface of the frame body on the surface of a photomask or reticle via an adhesive material.

  When foreign matter adheres to the surface of the photomask or reticle, the foreign matter forms an image on the photoresist formed on the semiconductor wafer, causing a circuit pattern defect. On the other hand, when a dust-proof film is placed on at least the pattern surface of a photomask or reticle, foreign matter adhering to the surface of the dust-proof film shifts the focus position, so that an image can be formed on the photoresist formed on the semiconductor wafer. In addition, the defect of the circuit pattern can be suppressed.

  However, the refractive index of a material such as a fluororesin or a cellulose derivative increases as the exposure wavelength becomes shorter, and light loss or flare / ghosting due to surface reflection becomes remarkable as it is. Further, there is a problem that the required high light transmittance cannot be secured in the ultraviolet and vacuum ultraviolet regions.

  A solution to these problems is to provide a moth-eye structure known as a non-reflective structure on the surface of the dust-proof film. In general, when light enters a light transmissive member formed by laminating two light transmissive materials having different refractive indexes (material 1 and material 2), the light is incident due to a difference in refractive index at the interface between material 1 and material 2. Part of the reflected light is reflected. In this case, the reflectance of incident light increases as the difference in refractive index increases. On the other hand, when a fine concavo-convex structure is provided at the interface between the light transmissive materials (material 1 and material 2), the reflectance of incident light at the interface is greatly reduced. In this case, due to the effective medium approximation between the light transmissive materials (material 1 and material 2), there is no step in the change in the refractive index at the interface, and the refractive index gradually changes. For this reason, there are no interfaces having substantially different refractive index differences, and the reflectance of incident light is reduced. If the reflection loss at the interface is reduced, the transmittance can be increased. A structure that suppresses reflection based on such a principle is called a moth-eye structure. For example, a quasi-hexagonal lattice pattern or a tetragonal lattice pattern in which convex portions are arranged to form a plurality of rows of tracks has been proposed ( Patent Document 1).

  As a method for forming a moth-eye structure on at least one surface of the dust-proof film, a nanoimprint method can be mentioned. This is a technology that allows a member subjected to fine pattern processing to be used as a mold (master), and can be easily transferred and copied to a resin (transfer material) with processing accuracy of several nm to several tens of nm.

  As a method for imparting a moth-eye structure to the dust-proof film by a nanoimprint method, for example, a master having a fine concavo-convex structure on the surface is prepared, and the dust-proof film or There is a method of peeling the stamper after sandwiching the dissolved dust-proof film raw material.

JP 2009-258752 A

  However, it is necessary to form the dust-proof film very thinly, and the surface doubling effect of the dust-proof film is added by the fine uneven structure provided on the surface of the dust-proof film. For this reason, in the conventional method of manufacturing a dustproof film, when a fine rugged structure is imparted to the surface of the dustproof film, when the dustproof film is peeled off from the stamper, In some cases, the film itself was broken, and it was difficult to peel off and isolate the dust-proof film from the stamper.

  In addition, with the recent increase in area of liquid crystal panels, it is desired to increase the area of dust-proof films for liquid crystal panels. In order to obtain a dust-proof film with a large area, it is necessary to transfer the fine relief structure over the large area to the surface of the dust-proof film, and a fine relief structure with an area equivalent to the area of the substrate when the dust-proof film is formed It is necessary to produce a stamper having

  However, there is no precedent for producing a nano-order fine concavo-convex structure on such a large-area silicon wafer or glass substrate using the conventional exposure interference method or electron beam drawing method, and a dust-proof film for liquid crystals having a moth-eye structure is not available. It was extremely difficult to produce.

  The present invention has been made in view of such points, and it is difficult for foreign matter to adhere to it, and a dustproof film excellent in antireflection performance and transmittance over a wide wavelength region can be obtained, and further, the area can be increased. In addition, an object of the present invention is to provide a method for producing a dustproof film with high productivity.

The method for producing a dust-proof film of the present invention includes a mold production step of producing a resin mold having a substrate and a cured resin layer provided on the substrate and having a fine uneven structure on the surface, and the fine unevenness of the resin mold. In a state where the structure forming surface and the uncured resin layer provided on the inorganic substrate are bonded together, the uncured resin layer is cured to form a cured resin layer, and then the cured resin layer is peeled from the resin mold, A resin mold manufacturing step of manufacturing a resin mold provided on the substrate and the inorganic substrate and having the cured resin layer on the surface of which the fine concavo-convex structure of the resin mold is transferred; and on the cured resin layer of the resin mold An uncured dustproof film material layer forming step for forming an uncured dustproof film material layer, and curing the uncured dustproof film material layer to form a dustproof film, and then peeling the dustproof film from the resin mold to form a dustproof film. A dust-proof film peeling step to be formed, and a fluorine element concentration (Es) in the surface portion of the cured resin layer of the resin mold on the fine concavo-convex structure forming surface side and an average fluorine concentration (Eb) in the cured resin layer The ratio satisfies the following formula (1).
Formula (1)
20 ≦ Es / Eb ≦ 200

  According to this method, since the resin mold is produced by transferring the fine concavo-convex structure of the resin mold, it is not necessary to use the exposure interference method or the electron beam drawing method for producing the resin mold. This makes it possible to produce a large-area resin mold having a moth-eye structure composed of a nano-order fine concavo-convex structure. And this resin mold, since the fluorine element concentration (Es) and the average fluorine concentration (Eb) in the resin layer in the surface portion of the cured resin layer on the fine concavo-convex structure surface side satisfy the above formula (1), A concentration gradient is formed from one surface side of the resin mold to the other surface side. Due to this concentration gradient, the fluorine concentration in the surface portion on the fine concavo-convex structure side becomes relatively higher than the average fluorine concentration (Eb) in the resin, so that the dust-proof film provided on the surface on the fine concavo-convex structure side from the resin mold Is easy to peel off. Thereby, even when a dustproof film having a fine relief structure is provided over a large area, the dustproof film can be peeled from the resin mold without damaging the fine relief structure. As a result, it is possible to realize a method for manufacturing a dustproof film that is difficult to adhere to foreign matter, has excellent antireflection performance and transmittance over a wide wavelength region, and has a high productivity that provides a dustproof film capable of increasing the area.

  The method for producing a dustproof film of the present invention includes an antireflection film laminating step of laminating an antireflection film layer on the dustproof film material layer between the dustproof film material layer forming step and the dustproof film peeling step. It is preferable.

  In the method for producing a dustproof film of the present invention, the fine concavo-convex structure of the dustproof film has a pillar shape including a plurality of conical, pyramidal, or elliptical cone-shaped projections, or a conical shape, a pyramidal shape, or an elliptical cone. It is a hole shape including a plurality of concave portions, the distance between adjacent convex portions is preferably 1 nm to 1000 nm, and the height of the convex portions is preferably 1 nm to 1000 nm.

  According to the present invention, a dust-proof film that hardly adheres to foreign matters, has an anti-reflection performance and an excellent transmittance over a wide wavelength region, can be increased in area, and has a high productivity. The manufacturing method can be realized.

It is the schematic of the manufacturing apparatus of the mold which concerns on this Embodiment. It is the schematic which shows an example of the manufacturing process of the dust-proof film | membrane which concerns on this Embodiment. It is the schematic which shows the other example of the manufacturing process of the dust-proof film | membrane which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the other example of the resin mold which concerns on this Embodiment.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the method for manufacturing a dust-proof film according to the present embodiment, a reel-shaped resin mold having a fine concavo-convex structure provided on the surface is manufactured, and the fine concavo-convex structure of the reel-shaped resin mold is transferred to a resin layer to thereby form a surface. A dustproof film having a fine uneven structure is manufactured.

(A) Mold Manufacturing Process First, an outline of a mold manufacturing apparatus used in the mold manufacturing process of the dustproof film manufacturing method according to the embodiment of the present invention will be briefly described. FIG. 1 is a schematic view of a manufacturing apparatus used in a mold manufacturing process according to the present embodiment.

  As shown in FIG. 1, the manufacturing apparatus includes an original fabric roll 101 around which a base material 11 is wound, and a take-up roll 102 that winds up a reel-shaped resin mold 12 manufactured using the base material 11. . Between the raw roll 101 and the take-up roll 102, a coating device 103 for applying a photocurable resin on the base material 11 from the upstream side to the downstream side in the transport direction of the base material 11, and the outer peripheral surface A cylindrical mold 104 having a fine concavo-convex structure, a pressurizing means 105 for bringing the photocurable resin on the substrate 11 and the outer peripheral surface of the cylindrical mold 104 into close contact, and the outer periphery of the cylindrical mold 104 A light source 106 for irradiating light onto the photocurable resin on the substrate 11 that is in close contact with the surface is provided in this order. In addition, when apply | coating photocurable resin using a solvent, you may use the transfer apparatus further provided with the drying furnace 107 which dries the solvent in photocurable resin.

  Next, with reference to FIG. 2, the manufacturing method of the dust-proof film | membrane which concerns on this Embodiment is demonstrated in detail. FIG. 2 is a schematic diagram illustrating an example of a manufacturing process of a dustproof film. First, a mold manufacturing process for manufacturing a reel-shaped resin mold used for manufacturing a dustproof film is performed by the manufacturing apparatus shown in FIG. As shown in FIG. 2A, in this mold manufacturing process, a photocurable resin is applied by a coating device 103 onto a light-transmitting base material 11 unwound from an original fabric roll 101 to form an uncured resin layer 13. To do.

  Next, in a state where the uncured resin layer 13 is brought into close contact with the outer peripheral surface of the cylindrical mold 104 by the pressurizing means 105 while rotating the cylindrical mold 104 having a fine uneven structure on the outer peripheral surface, Is irradiated to the uncured resin layer 13 from the substrate 11 side. As a result, the photocurable resin of the uncured resin layer 13 is photocured, and the cured resin layer 14 having the fine uneven structure provided on the outer peripheral surface of the cylindrical mold 104 transferred to the surface is obtained. As a result, as shown in FIG. 2B, a reel-shaped resin provided with a light-transmitting base material 11 and a cured resin layer (photo-curable resin layer) 14 provided on the base material 11 and having a fine uneven structure on the surface. A mold 12 is produced. Next, the produced reel-shaped resin mold 12 is taken up by the take-up roll 102. In the mold manufacturing process, a protective film (cover film) may be laminated on the cured resin layer 14 in order to protect the fine concavo-convex structure transferred from the cylindrical mold 104.

  Next, as shown in FIG. 2C, a resin mold manufacturing process is performed in which the resin mold 15 is manufactured using the manufactured reel-shaped resin mold 12. In this resin mold manufacturing process, an uncured resin layer 17 provided by applying a photocurable resin on the surface of the inorganic substrate 16 is bonded to the fine uneven structure on the surface of the cured resin layer 14 of the reel-shaped resin mold 12. Then, by irradiating the uncured resin layer 17 with light from the reel-shaped resin mold 12 side and photocuring the uncured resin layer 17, the cured resin in which the fine concavo-convex structure on the surface of the reel-shaped resin mold 12 is transferred to the surface Layer 18 is formed. As a result, the resin mold 15 provided with the inorganic substrate 16 and the cured resin layer 18 provided on the inorganic substrate 16 and having a fine uneven structure on the surface is obtained. The cured resin layer 18 of the resin mold 15 has a concentration gradient of fluorine concentration in which the fluorine concentration increases from the surface 18A side on the inorganic substrate 16 side toward the fine uneven structure forming surface 18B.

  Next, the resin mold 15 is peeled off from the reel-shaped resin mold 12 to obtain the resin mold 15 having the fine uneven structure of the reel-shaped resin mold 12 transferred on the surface. The fine concavo-convex structure of the resin mold 15 has a shape obtained by inverting the fine concavo-convex structure of the reel-shaped resin mold 12.

  Next, as shown in FIG. 2D, a dust-proof film material layer forming step is performed. In this dust-proof film material layer forming step, the uncured dust-proof film material is dissolved in a solvent on the fine concavo-convex structure on the surface 18B of the cured resin layer 18 of the resin mold 15, and is applied and dried to uncured dust-proof film material. Layer 19 is formed.

  Next, as shown in FIG. 2D, a dustproof film peeling step is performed. In this dustproof film peeling step, the resin mold 15 and the uncured dustproof film material layer 19 are heated, and the uncured dustproof film material layer 19 is heat cured. Then, as shown in FIG. 2E, after the uncured dustproof film material layer 19 is sufficiently heat-cured to become the dustproof film 20, the dustproof film 20 is obtained by peeling the dustproof film 20 from the resin mold 15. Here, in the cured resin layer 18 of the resin mold 15, the fluorine concentration of the surface 18 </ b> B on the fine concavo-convex structure side is relatively higher than the surface 18 </ b> A on the inorganic substrate 16 side. The cured resin layer 18 can be prevented from being peeled off from the inorganic substrate 16.

  In the dust-proof film manufacturing process described above, as shown in FIGS. 3A to 3C, an anti-reflection film is formed on the uncured dust-proof film material layer 19 between the dust-proof film material layer forming process and the dust-proof film peeling process. An antireflection film laminating step for laminating 21 may be performed. In this antireflection film laminating step, an antireflection film material is applied on the uncured dustproof film material layer 19 and dried to provide an antireflection film 21, and then the uncured dustproof film material layer 19 and the antireflection film 21 are coated. Heat cure. Alternatively, after the uncured dustproof film material layer 19 is thermally cured, the antireflection film material may be applied and dried to provide the antireflection film 21, and the antireflection film 21 may be thermally cured. Then, after the uncured dust-proof film material layer 19 is sufficiently heat-cured to become the dust-proof film 20, the anti-reflection film 21 and the dust-proof film 20 are peeled off from the resin mold 15 so as to be opposite to the surface having the fine uneven structure. The dust-proof film 20 in which the antireflection film 21 is laminated on the main surface on the side can be obtained.

  In the embodiment described above, the resin mold 15 can be used again in the dust-proof film material layer forming step after the dust-proof film peeling step. In addition, by performing the resin mold manufacturing process using the resin mold 15, a shape in which the fine uneven structure on the surface of the resin mold 15 is inverted, that is, a fine uneven structure corresponding to the fine uneven structure of the reel-shaped resin mold 12 is obtained. It is also possible to produce a resin mold having the same.

  Next, materials used in each step and conditions of each step in the method for manufacturing a dustproof film according to the present embodiment will be described in detail.

(A) Mold manufacturing process (light transmissive substrate)
The substrate 11 is not particularly limited as long as it has as a main component a material that is substantially light transmissive with respect to a light source used in the ultraviolet / visible light region, but a resin excellent in handling property and workability. A material is preferred. Further, as the substrate 11, a transparent sheet using a resin material may be used.

  Examples of the resin material used for the substrate 11 include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cycloolefin resin (COP), crosslinked polyethylene resin, polyvinyl chloride resin, polyarylate resin, polyphenylene ether resin, modified Amorphous thermoplastic resins such as polyphenylene ether resin, polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, triacetyl cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate There are crystalline thermoplastic resins such as phthalate resin, polyethylene resin, polypropylene resin, polybutylene terephthalate resin, aromatic polyester resin, polyacetal resin, and polyamide resin. It is preferably Lum or sheet form. The surface of the substrate 21 (transparent sheet) can be subjected to primer treatment, atmospheric pressure plasma treatment, and corona treatment in order to improve adhesion with the photocurable resin.

  In the mold production process, the uncured resin layer 13 on the substrate 11 is irradiated with light and photocured in a state of being in close contact with the cylindrical mold 104. For this reason, although it depends on the photocurable resin to be used, the substrate 11 is required to have good transmittance in the range of 200 nm to 500 nm. Depending on the photosensitivity of the photocurable resin to be used, the specific transmittance value is not particularly limited in the range of 200 nm to 500 nm. If the 365 nm, 405 nm and total light transmittance are good, the photocuring is performed. Is preferable because the photosensitive resin 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.

(Cured resin layer)
The cured resin layer 14 contains a photocurable resin. The photo-curing resin is transferability, peelability from the cylindrical mold, adhesion to the substrate 11, viscosity, film-forming properties, photosensitivity, mechanical properties after curing, and a cured resin layer when the resin mold 15 is produced. 18 is selected in consideration of the releasability with respect to 18.

  The cured resin layer 14 used in the mold manufacturing process has a fluorine element concentration in the surface portion (hereinafter also referred to simply as “surface portion”) of the surface (hereinafter also referred to as “fine concavo-convex structure forming surface”) on which the fine concavo-convex structure is formed. (Es) is preferably higher than the average fluorine element concentration (Eb) in the cured resin layer 14. With this configuration, the fluorine element concentration (Es) on the fine uneven structure forming surface side in the cured resin layer 14 is relatively higher than the average fluorine element concentration (Eb) in the cured resin layer 14. The releasability between the reel-shaped resin mold 12 and the resin mold 15 in a certain resin mold manufacturing process is improved.

  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 (meth) ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, phen Xylethyl (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, tert-butyl (meth) ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, silicone-based acrylate compounds, and the like. 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 releasability of the reel-shaped resin mold 12 from the cylindrical mold 104 in the mold manufacturing process is improved. This also has the same effect when releasing the mold after bonding the reel-shaped resin mold 12 and the resin mold 15 in the resin mold manufacturing process.

  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.

  By using a fluorine-containing (meth) acrylate having a functional group as the photocurable resin, the adhesiveness between the cured resin layer 14 and the substrate 11 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 of a 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 surface of the cured resin layer 14 on which the fine concavo-convex structure is formed can be further lowered, the adhesion between the cured resin layer 14 and the substrate 11 is improved. Moreover, since the average fluorine element density | concentration (Eb) in the cured resin layer 14 can be decreased and the intensity | strength of the cured resin layer 14 can be maintained, since repeat transferability improves more, it is preferable. As such urethane (meth) acrylate, for example, “OPTOOL DAC” manufactured by Daikin Industries, Ltd. can be used.

（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。）
化学式（２）
Ｆ（ＣＦ_２）_６ＣＨ_２ＣＨ_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２

(In the chemical formula (1), R1 represents the following chemical formula (3), and R2 represents the following chemical formula (4).)
Chemical formula (2)
_{F (CF 2) 6 CH 2} CH 2 OCOC (CH 3) = CH 2

（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. )

  A fluorine-containing (meth) acrylate may be used individually by 1 type, and may use 2 or more types 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; S series: FTX-207S, FTX-211S, FTX-220S, 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-trimethylbenzoyldiphenylphosphine 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 thickness and viscosity of the photocurable resin, and are not limited. For example, the solvent is added to 100 parts by weight of the photocurable resin. 1 part by weight to 10000 parts by weight can be added.

  A coating method using a known coating coater or impregnation coating coater can be used as a method for coating the photocurable resin onto the substrate 11 by the coating apparatus 103. Specific examples include coating 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. Moreover, these coating methods may be implemented by a single wafer method or a continuous method. It is preferable to apply by a continuous method from the viewpoint of productivity. A continuous coating method using a dip coater, comma knife coater, gravure coater or laminator is particularly preferred.

The light source 106 used for irradiating the cured resin layer 14 with light is not particularly limited, and various light sources can be used depending on applications and facilities. As the light source 106, 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.

  In the mold manufacturing process, the pressing means 105 for press-bonding the cylindrical mold 104 and the uncured resin layer 13 causes the cylindrical mold 104 and the uncured resin layer 13 to adhere to the uncured resin layer 13. Light cure by light irradiation. The fine concavo-convex structure on the outer peripheral surface of the cylindrical mold 104 is accurately transferred by irradiating and transferring light while the fine concavo-convex structure on the outer peripheral surface of the cylindrical mold 104 is in close contact with the uncured resin layer 13. Can be transferred. In addition, by performing transfer in a state where the fine uneven structure on the outer peripheral surface of the cylindrical mold 104 and the uncured resin layer 13 are in close contact with each other, insufficient curing due to oxygen can be avoided.

  Further, in the mold manufacturing process, it is preferable to perform light irradiation by bringing the cylindrical mold 104 and the uncured resin layer 13 into close contact with each other in a nitrogen atmosphere. Thereby, contact of oxygen in the atmosphere with the photocurable resin of the uncured resin layer 13 can be avoided, and inhibition of the photopolymerization reaction by oxygen can be reduced, so that the cured resin layer 14 can be sufficiently cured. This is preferable because it is possible.

  In order to irradiate light by bringing the uncured resin layer 13 and the cylindrical mold 104 into close contact with each other, the uncured resin layer 13 and the cylindrical mold 104 are directly pressed by a nip roll as the pressurizing means 105 and light is applied. In the state where the uncured resin layer 13 and the cylindrical mold 104 are pressure-bonded by controlling the tension of the base material 11 by controlling the unwinding of the raw roll 101 and the winding roll 102. You may irradiate light. In these cases, the pressing pressure and tension can be appropriately adjusted depending on the transferability of the uncured resin layer 13.

  In the example described above, an example in which a photocurable resin is used to form the uncured resin layer 13 has been described. However, the uncured resin layer 13 may be, for example, photocured, thermally cured, cured by an electron beam, and microscopic. Various curable resins that are cured by waves or the like can be used. Among these, it is preferable to use a photocurable resin. After applying the photocurable resin to the substrate 11 by the above application method, the photocurable resin can be irradiated with light with an arbitrary amount of light at a predetermined wavelength, thereby promoting the curing reaction of the photocurable resin. In the case where a photocurable resin is not used as the curable resin, it is not always necessary to use the light transmissive substrate 11.

  In the mold manufacturing process, it is not always necessary to use a cylindrical mold as a mold for transferring the fine concavo-convex structure to the uncured resin layer 13, but a cylindrical mold is used from the viewpoint of continuous productivity and yield. 104 is preferably used. A seamless cylindrical mold 104 is more preferable. In the case where there is a seam, a portion where there is no pattern of the seam portion is cut off, so that not only the yield is deteriorated but also the work of cutting is excessive, and the continuous productivity is also deteriorated.

  In addition, as the cylindrical mold 104, a cylindrical mold 104 having a fine concavo-convex structure corresponding to the shape of the fine concavo-convex structure provided on the outer surface of the dust-proof film is used. The fine concavo-convex structure of the cylindrical mold 104 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 form directly on the outer peripheral surface of a base material. Among these, from the viewpoint of obtaining a cylindrical mold 104 that is seamless in a fine uneven shape, a photolithography method, a direct drawing lithography method using a semiconductor laser, an interference exposure method, an electroforming method, and an anodizing method are preferable. A direct drawing lithography method using a laser, an interference exposure method, and an anodic oxidation method are more preferable.

  Also, as the cylindrical mold 104, the fine uneven 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 104 with high positional accuracy. May be used. Alternatively, a fine concavo-convex 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.

  As the cylindrical mold 104, it is desirable to use a mold that can easily form a fine uneven structure and has excellent durability. From such a viewpoint, the cylindrical mold 104 is preferably 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).

  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 104. By performing the mold release treatment, the surface free energy of the cylindrical mold 104 can be reduced. Therefore, even when continuously transferred to a photo-curable resin, good releasability and pattern shape of a fine relief structure Can be held. 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 appropriately selected depending on the type of material of the cylindrical mold 104 and the combination with the photocurable resin to be transferred. it can.

(B) Resin mold preparation process As resin for resin molds, the photocurable resin used for the mold preparation process can be used. As described above, the cured resin layer 18 formed of the photo-curable resin has a surface portion (hereinafter simply referred to as “fine concavo-convex structure forming surface 18B”) on which the fine concavo-convex structure is formed (hereinafter, simply referred to as “fine concavo-convex structure forming surface 18B”). The fluorine element concentration (Es) in the “surface portion”) has a concentration gradient higher than the average fluorine element concentration (Eb) in the cured resin layer 18.

In the method for producing a dustproof film according to the present embodiment, the ratio of the fluorine element concentration (Es) in the surface portion of the cured resin layer 18 to the average fluorine element concentration (Eb) in the cured resin layer 18 is expressed by the following formula (1). Meet. With this configuration, the fluorine element concentration (Es) in the surface portion of the cured resin layer 18 on the fine concavo-convex structure forming surface side is sufficiently higher than the average fluorine element concentration (Eb) in the cured resin layer 18. Thereby, since the free energy of the fine concavo-convex structure forming surface of the cured resin layer 18 is further reduced, the releasability between the cured resin layer 18 and the dustproof film 20 is improved. As a result, even when the dust-proof film 20 having a small film thickness and a large area is manufactured, the dust-proof film 20 is not broken from the cured resin layer 18 without breaking or breaking the dust-proof film 20 and destroying the fine uneven structure of the dust-proof film 20. Therefore, it is difficult for foreign matter to adhere to the film, and a dustproof film excellent in antireflection performance and transmittance over a wide wavelength region can be obtained. And since the average fluorine element density | concentration (Eb) in the cured resin layer 18 becomes relatively low with respect to the fluorine element density | concentration (Es) in the surface part of the cured resin layer 18, the intensity | strength of the cured resin layer 18 itself improves. In addition, the free energy can be kept high on the surface 18A of the cured resin layer 18 on the inorganic substrate 16 side. Thereby, the adhesiveness between the inorganic substrate 16 and the cured resin layer 18, the release property of the dust-proof film from the cured resin layer 18, and the repetitive transfer property are further improved. Thereby, the releasability of the dustproof film 20 from the cured resin layer 18 and the adhesion between the cured resin layer 18 and the inorganic substrate 16 are further improved.
Formula (1)
20 <Es / Eb ≦ 200

  When a large amount of fluorine component is introduced into the entire cured resin layer 18, the surface fluorine element concentration (Es) reaches a certain value from the viewpoint of segregation density, and the average fluorine element concentration (Eb) increases. Therefore, the value of Es / Eb tends to decrease. On the other hand, when a very small amount of fluorine component is introduced into the entire cured resin layer 18, most of the fluorine component is segregated on the surface. Therefore, the average fluorine element concentration (Eb) in the resin shows a small value, and the value of Es / Eb tends to increase. However, even in these cases, a peeling function capable of satisfactorily releasing the dust-proof film can be obtained by making the range satisfying the above formula (1).

  In addition, the thickness of the cured resin layer 18 is not particularly limited as long as the adhesion to the inorganic substrate 16 can be secured. The thickness of the cured resin layer 18 is preferably 1 mm or less from the viewpoint of preventing the occurrence of large millimeter-scale waviness on the surface.

  The cured resin layer 18 may have any fluorine concentration gradient as long as it satisfies the above formula (1). For example, the concentration gradient may be continuously steplessly changed from the surface 18A on the inorganic substrate 16 side of the cured resin layer 18 toward the fine concavo-convex structure forming surface 18B, and stepwise changes stepwise. You may do. Further, in the thickness direction from the surface 18A on the inorganic substrate 16 side of the cured resin layer 18 to the fine concavo-convex structure forming surface 18B, a concentration gradient from the surface 18A on the inorganic substrate 16 side to the central portion of the cured resin layer 18, and the cured resin The concentration gradient from the center of the layer 18 to the fine relief structure forming surface 18B may be the same or may have a different concentration gradient.

  Further, as the cured resin layer 18, the free energy of the surface of the cured resin layer 18 on which the fine concavo-convex structure is formed is lower in the range of 26 ≦ Es / Eb ≦ 189 within the range of the above formula (1). The repetitive transfer property is particularly preferable. Further, the cured resin layer 18 preferably satisfies 30 ≦ Es / Eb ≦ 160, more preferably 31 ≦ Es / Eb ≦ 155, and 46 ≦ Es / Eb ≦ 155 within the range of the above formula (1). If it exists, since the said effect can be expressed further, it is especially preferable.

  In the present specification, the “surface portion of the cured resin layer 18” refers to the surface portion of the fine uneven structure of the cured resin layer 18, and in the thickness direction orthogonal to the surface of the cured resin layer 18, the cured resin. It means a portion in the range of about 1% to about 10% or a portion in the range of 2 nm to 20 nm from the surface side of the layer 18. The “surface portion of the cured resin layer 18” includes a range in which a specific region having a relatively high average fluorine concentration exists with respect to the average fluorine concentration (Eb) of the entire cured resin layer 18. For this reason, it is not always necessary that a specific region having a high average fluorine concentration (Es) be present over the entire surface of the cured resin layer 18 on the fine concavo-convex structure forming surface side. In the present invention, the fluorine element concentration (Es) in the surface portion of the cured resin layer 18 employs a value obtained by scanning X-ray photoelectron spectroscopy (XPS method). 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.

  Further, in this specification, “average fluorine element concentration (Eb) in the cured resin layer 18” is a value calculated from the charged amount, a value analyzed from a gas chromatograph mass spectrometer (GC / MS), or an ion chromatogram. The value analyzed from the graph analysis is adopted. That is, it means the fluorine element concentration contained in the entire cured resin layer 18. For example, a section of a resin mold composed of a cured product of a photopolymerizable mixture formed into a film and having a resin part physically peeled off is decomposed by a flask combustion method and subsequently subjected to ion chromatography analysis. Thus, the average fluorine element concentration (Eb) in the resin can be identified.

  As shown in FIG. 4, the resin mold 15 may have an adhesive layer 22 for bonding the inorganic substrate 16 and the cured resin layer 18 between the inorganic substrate 16 and the cured resin layer 18. . By providing the adhesive layer 22, the adhesion between the inorganic substrate 16 and the cured resin layer 18 is further improved.

The material of the inorganic substrate 16 for the resin mold 15 is preferably a material that can ensure sufficient flatness, such as synthetic quartz, fused quartz, alkali-free glass, low alkali glass, soda lime glass, silicon, nickel plate, and the like. . Use of these is preferable because the flatness of the substrate surface with high accuracy can be secured. Further, considering that the inorganic substrate 16 may be cracked due to temperature unevenness when the dust-proof film is dried, which will be described later, it is preferable that the inorganic substrate 16 has a smaller thermal expansion coefficient. In particular, the linear expansion coefficient at 0 ° C. to 300 ° C. is preferably 50 × 10 ⁻⁷ m / ° C. or less. The convex shape or concave shape on the surface of the inorganic substrate 16 may have a shape corresponding to the convex structure described above.

  By subjecting the inorganic substrate 16 to a surface treatment, adhesion between the inorganic resin substrate 16 and the cured resin layer 18 is improved. As the surface treatment, adhesive coating, surface treatment agent, silane coupling agent, UV ozone cleaning, plasma cleaning and the like can be appropriately selected. These surface treatments can also be used in combination. Particularly preferred surface treatment is silane coupling agent or adhesive coating.

  Silane coupling agents include functional groups such as acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, acrylic group, methacryl group, vinyl group, epoxy group, glycidyl group, allyl group, oxetanyl group, etc. Is preferable. In particular, when it is any one of (meth) acrylic group, (meth) acryloyl group, (meth) acryloxy group, epoxy group, glycidyl group, and oxetane group, the adhesiveness to inorganic substrate 16 and the adhesiveness to resin mold Is preferable because it becomes better. As these silane coupling agents, for example, KBM-1003 (made by Shin-Etsu Silicone) which is vinyltrimethoxysilane, KBE-1003 (made by Shin-Etsu Silicone) which is vinyltriethoxysilane, SZ which is vinyltrimethoxysilane. -6300 (made by Toray Dow Corning), SZ-6075 (made by Toray Dow Corning) which is vinyltriacetoxysilane, TSL8310 (made by GE Toshiba Silicone) which is vinyltrimethoxysilane, TSL8311 (made by GE Toshiba Silicone) GE Toshiba Silicone), KMB-502 (made by Shin-Etsu Silicone) which is 3-methacryloxypropylmethyldimethoxysilane, KMB-503 (made by Shin-Etsu Silicone) which is 3-methacryloxypropyltrimethoxysilane, 3-Methacryl KME-502 (made by Shin-Etsu Silicone) which is loxypropylmethyldiethoxysilane, KBM-503 (made by Shin-Etsu Silicone) which is 3-methacryloxypropyltriethoxysilane, SZ- which is γ-methacryloxypropyltrimethoxysilane 6030 (manufactured by GE Toshiba Silicone), TSL8370 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropyltrimethoxysilane, TSL8375 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropylmethyldimethoxysilane, 3-acrylic KBM-5103 (made by Shin-Etsu Silicone) which is loxypropyltrimethoxysilane, KBM-303 (made by Shin-Etsu Silicone) which is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Zimetoki Silane KBM-402 (manufactured by Shin-Etsu Silicone), 3-glycidoxypropyltrimethoxysilane KBM-403 (manufactured by Shin-Etsu Silicone), 3-glycidoxypropylmethyldiethoxysilane KBE-402 ( Shin-Etsu Silicone Co., Ltd.), 3-glycidoxypropyltriethoxysilane KBE-403 (Shin-Etsu Silicone Co., Ltd.), p-styryltrimethoxysilane KBM-1403 (Shin-Etsu Silicone Co., Ltd.), and the like.

  The silane coupling agent to be used and the adhesive layer 22 can contain a photopolymerization initiator that can be used in the mold production process. A photoinitiator causes a radical reaction or an ionic reaction by light. The photopolymerization initiator used is preferably a photopolymerization initiator that causes a radical reaction from the viewpoint of reaction rate.

  The film thickness of the silane coupling agent and the adhesive layer 22 is preferably 3 μm from the monomolecular layer, and more preferably 1 μm from the monomolecular layer. A thickness of 500 nm from the monomolecular layer is preferable because the film thickness uniformity of the adhesive layer 22 becomes better.

  As the adhesive layer 22, various commercially available adhesives can be used. As the adhesive layer 22, for example, an epoxy adhesive, an acrylate adhesive, a methacrylate adhesive, an isocyanate adhesive, a silicone adhesive, or the like can be used. Further, these adhesives may be used in combination with a photocurable resin. Moreover, these may be used independently and multiple types may be used. From the viewpoint of good adhesion to an inorganic material, it is preferable to use an epoxy adhesive or a silicone adhesive as the adhesive layer 22.

  Further, as the adhesive layer 22, a layer containing functional fine particles can be used for imparting functionality such as strength improvement. Examples of the functional fine particles include metal oxides, metal fine particles, and carbon-based fine particles. Examples of the metal oxide include silica, titania, zirconia, ceria, alumina, zinc oxide, and tin oxide. Examples of the carbon-based fine particles include carbon black, carbon nanotube, and fullerene. Examples of the shape of the functional fine particles include a spherical shape, a granular shape, a rod shape, a needle shape, a hollow shape, and a random shape, and these may have a surface modification such as a silane coupling agent on the fine particle surface.

  In the resin mold manufacturing process, an uncured resin layer 17 is formed on the main surface of the inorganic substrate 16, and the fine uneven structure of the reel-shaped resin mold 12 is transferred to the surface of the formed uncured resin layer 17. The resin mold is released from the cured resin layer 18 to which is transferred.

  The uncured resin layer 17 is formed by applying the above-described photopolymerizable resin or the like on the inorganic substrate 16 by spin coating or bar coating. The uncured resin layer 17 can be formed by, for example, a dipping method, a casting method, a spin coating method, a bar coating method, a die coating method, or the like.

  When the uncured resin layer 17 is formed, the inorganic substrate 16 is subjected to ozone treatment, oxygen ashing treatment, piranha solution, KOH solution, piranha solution or KOH solution and ultrasonic treatment as necessary. Surface treatment may be performed by treatment or the like. By such surface treatment, the surface of the inorganic substrate 16 is activated, and the adhesion between the cured resin layer 18 and the inorganic substrate 16 is improved.

  When transferring the fine uneven structure to the uncured resin layer 17, the reel-shaped resin mold 12 is uncured resin so that the surface of the uncured resin layer 17 and the surface of the reel-shaped resin mold 12 are opposed to each other. A laminate of the reel-shaped resin mold 12 / uncured resin layer 13 / inorganic substrate 16 is bonded to the layer 17. Then, the uncured resin layer 17 is cured by UV irradiation or heating to form a cured resin layer 18, whereby the fine uneven structure of the reel-shaped resin mold 12 is transferred to the surface of the cured resin layer 18. The reel-shaped resin mold 12 is not particularly limited as long as it is a reel-shaped resin mold 12 made of a fluorine-containing resin, but more preferably contains a photopolymerizable mixture in the same manner as the cured resin layer 18. Is preferred.

  When transferring the fine concavo-convex structure to the uncured resin layer 17, the fine concavo-convex structure forming surface of the reel-shaped resin mold 12 is pressed against the surface of the uncured resin layer 17, or the pressure is released after being pressed. , UV irradiation or heating is preferable because the transfer accuracy and the film thickness accuracy of the cured resin layer 18 are improved. The pressing pressure when pressing the reel-shaped resin mold 12 against the uncured resin layer 17 is preferably more than 0 MPa to 10 MPa, more preferably 0.01 MPa to 5 MPa, and further preferably 0.01 MPa to 1 MPa.

  In addition, when UV irradiation is performed when transferring the fine concavo-convex structure to the uncured resin layer 17, it is preferable to perform a heat treatment after the UV irradiation. By performing this heat treatment, unreacted groups in the photopolymerizable mixture constituting the uncured resin layer 17 can be reduced, and release is facilitated. As temperature of heat processing, 50 to 120 degreeC is preferable, 50 to 105 degreeC is more preferable, and 60 to 105 degreeC is further more preferable. The heating time for the heat treatment is preferably 15 seconds to 10 minutes, more preferably 15 seconds to 5 minutes, and even more preferably 30 seconds to 5 minutes.

  When the resin mold 15 is released, the reel-shaped resin mold 12 is peeled from the cured resin layer 18 of the laminate. When the resin mold 15 is peeled off, heat treatment may be performed after the reel-shaped resin mold 12 is peeled off. By this heat treatment, the reaction of unreacted groups in the photopolymerizable mixture constituting the cured resin layer 18 is promoted, so that the releasability of the reel-shaped resin mold 12 from the cured resin layer 18 is improved. Furthermore, since the resin mold stable at the heating temperature can be obtained by the heat treatment, when the resin mold 15 is transferred to the transfer material, the penetration of the resin material from the resin mold 15 to the transfer material is suppressed, and the resin mold 15 releasability is improved.

  As temperature of heat processing, 50 to 250 degreeC is preferable and 105 to 200 degreeC is more preferable. The heating time for the heat treatment is preferably 30 seconds to 60 minutes, more preferably 5 minutes to 60 minutes, and even more preferably 10 minutes to 30 minutes.

  When manufacturing the resin mold 15 having the adhesive layer 22 between the inorganic substrate 16 and the cured resin layer 18, the adhesive layer 22 is formed by coating or the like before the uncured resin layer 17 is formed. For example, when a silane coupling agent is used as the adhesive layer 22, the pH of the solution is adjusted as necessary after diluting the silane coupling agent or a mixture of the silane coupling agent and the photopolymerization initiator with a solvent. The hydrolysis reaction is accelerated in the lowered state, and the solution is applied onto the inorganic substrate 16. Then, the solvent is volatilized to form an adhesive layer. Examples of the method for forming the adhesive layer 22 include dipping, casting, spin coating, bar coating, and die coating. As temperature at the time of volatilizing a solvent, 20 to 200 degreeC is preferable and 60 to 180 degreeC is more preferable. Alternatively, the adhesive layer 22 may be formed by exposing the inorganic substrate 16 to vapor of a silane coupling agent to form a monomolecular film.

  In the above-described embodiment, the example in which the resin mold 15 is formed by applying the uncured resin layer 17 on the inorganic substrate 16 has been described. However, the resin mold 15 is uncured on the film base material. A reel-shaped resin mold on which a resin layer is formed can be bonded to an inorganic substrate. In this case, the film substrate of the reel-shaped resin mold may be selected based on environmental resistance using a resin mold. For example, in applications that undergo a process of volatilizing a high-boiling solvent, examples of the film substrate include PC (polycarbonate), PI (polyimide), PES (polyethersulfone), and PEN (polyethylene naphthalate).

  The resin mold 15 is variously used not only in dust-proof film applications but also in nanoimprint applications. The resin mold 15 is used, for example, when manufacturing for optical devices such as a microlens array, a wire grid type polarizing element, a moth-eye type non-reflective film, a diffraction grating, and a photonic crystal element, and nanoimprint applications such as patterned media. . In addition, it can be used for production of biodevices such as cell culture sheets, fat culture chips, and biosensor electrodes. In addition, it can be applied to the manufacture of various battery and capacitor electrodes, micro / nano channels, heat dissipation surfaces, heat insulation surfaces, and the like.

(C) Dust-proof film material layer forming step The material of the dust-proof film 20 is not particularly limited. The material of the dustproof film 20 is preferably a material having a high light transmittance at the exposure wavelength at which the dustproof film 20 is used. For example, cellulose derivatives (nitrocellulose, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc., or These are mixtures of two or more), cycloolefin resins (norbornene polymers or copolymers (including hydrogenated ones), such as Apel (registered trademark) (Mitsui Chemicals), Topas (registered trademark) (Manufactured by Polyplastics), Zeonex (registered trademark) or ZEONOR (registered trademark) (manufactured by Nippon Zeon), Arton (registered trademark) (manufactured by JSR), etc.), fluorine-based resin (tetrafluoroethylene-vinylidene fluoride) -Hexafluoropropylene) terpolymer, perfluoroal Such as DuPont's Teflon AF (registered trademark), Asahi Glass's Cytop (trade name), Augmont's Algoflon (trade name), etc. Use is conceivable. Among these resins, when a fluororesin having a perfluoroalkyl ether ring structure, cellulose acetate propionate or cycloolefin resin is used as a main component of an antireflection film material and a convex structure (dustproof film), it is dustproof. The formability of the film 20 and the concavo-convex structure is good and particularly preferable. The main component means that the amount of the target resin component contained in the dustproof film material is 50% by weight or more.

  The material of the antireflection film 21 may be the same as the material of the dustproof film, or may be a material. A concavo-convex structure formed of a different material, that is, a material different from the antireflection film 21 on the antireflection film 21. It is good also as a structure which provided the uneven | corrugated structure layer (dust-proof film material) which has. As a material of the antireflection film 21, for example, perfluorotributylamine can be used in addition to the above-described dustproof film material. Moreover, as a material of the antireflection film 21, it is preferable that the film material of the antireflection film and the material of the concavo-convex structure layer are the same from the viewpoint of manufacturing simplicity. The dust-proof film 20 having a concavo-convex structure layer on the antireflection film 21 can be produced by applying a dust-proof film material to a predetermined film thickness on a resin mold 15 having an upward convex structure.

  For the production of the dustproof film 20, it is preferable to use a polymer solution obtained by dissolving a dustproof film material in an organic solvent. With respect to the solvent, those that have very little volatilization at ambient temperature and that have a boiling point that is not too high are preferred. Considering the above, it is desirable that the solvent has a boiling point of 100 to 200 ° C.

  Examples of such a solvent include aliphatic hydrocarbon compounds, aromatic compounds, halogenated hydrocarbons such as chlorinated hydrocarbons, ester compounds, and ketone compounds. Of these, organic solvents such as saturated aliphatic hydrocarbon compounds such as alicyclic hydrocarbons, aromatic compounds, and halogenated hydrocarbons can be suitably used for cycloolefin resins, and chlorine for cellulose derivatives. Soluble in single or mixed organic solvents such as hydrocarbons, ketones, esters, alkoxy alcohols, benzene, alcohols. Examples of these organic solvents include organic solvents such as chlorinated hydrocarbons, ester compounds, and ketone compounds. As the chlorinated hydrocarbon, methylene chloride, ethylene chloride, propylene chloride and the like are preferably used, and as the ketone compound organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferably used. As the ester compound organic solvent, acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.) and lactate esters (ethyl lactate, butyl lactate, etc.) are preferably used. In addition, benzene, ethanol, methanol, cellosolve acetate, carbitol and the like can be used as a single or mixed solvent. The polymer solution in which the dust-proof film material is dissolved preferably has an absorbance of 0.05 or less in order to increase the light transmittance of the dust-proof film and to reduce foreign matter in the dust-proof film.

  The method for forming the dust-proof film and the method for producing the concavo-convex structure are not particularly limited, such as a spin coating method, a roll coating method, a knife coating method, and a casting method. From the viewpoint of uniformity and foreign matter management, the spin coating method is used. Is preferred. Hereinafter, the film forming method by the spin coat method will be described.

  The film thickness of the dustproof film 20 and the flatness of the film are mainly determined by the liquid temperature of the polymer solution, the ambient temperature / humidity, and the rotational speed of the resin mold. The temperature of the polymer solution is preferably about the same as the ambient temperature (10 to 30 ° C.), and the temperature of the resin mold 15 is preferably about the same as the ambient temperature. It is preferable that the liquid temperature, the ambient temperature, and the temperature of the resin mold 15 be approximately the same because the film thickness unevenness can be suppressed. The humidity is preferably 30% to 60%. After a suitable amount of polymer solution is dropped on the resin mold 15, the resin mold 15 is rotated at a rotational speed of 50 to 5000 rotations to form a film.

  The film thickness of the dustproof film 20 is preferably about 0.2 μm to 10 μm, and preferably 1 μm to 8 μm from the strength of the dustproof film 20 and the ease of forming a uniform film. When the concavo-convex structure is provided only on one surface of the dust proof film 20, the film thickness of the dust proof film 20 refers to the distance from the top of the convex portion of the concavo-convex structure to the opposite surface of the concavo-convex structure forming surface. In the case of being provided on both surfaces of the dustproof film 20, it indicates the shortest distance among the distances from the top of the convex portion of the concavo-convex structure on one surface to the top of the convex portion of the concavo-convex structure on the other surface.

  After the polymer solution is applied onto the resin mold 15, heat treatment can be performed to remove the solvent. As temperature of a heating process, 60 to 105 degreeC is preferable and 70 to 90 degreeC is more preferable. You may heat-process at another temperature after a heating process. The time for the heating treatment is preferably 1 minute to 10 minutes, more preferably 3 minutes to 7 minutes. As temperature of heat processing, 150 to 200 degreeC is preferable and 170 to 190 degreeC is more preferable. The time for the heat treatment is preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

(D) Dust-proof film peeling process After application, the resin mold 15 is placed in a heated oven or on a hot plate and dried to volatilize the solvent. After the film is dried, the film is peeled off from the resin mold 15. At this time, since stress is applied to the film, the dustproof film 20 and the antireflection film 21 are preferably extensible. Moreover, two sheets of the flat surface of the dust-proof film | membrane 20 produced similarly to the flat surface of the peeled-off dust-proof film | membrane 20 can be bonded together. Since the fine concavo-convex structure is formed on both surfaces, it is possible to manufacture the dust-proof film 20 having excellent transmittance and less dependency of the transmittance on the incident angle.

  When designing a fine concavo-convex structure on the surface of the dust-proof film 20, in the case of improving the transmittance and reducing the incident angle dependency, the wavelength and the distribution of the light emitted from the light source are all taken into account, such as the pitch and height. The structure needs to be determined. In particular, in order to further exhibit optical performance, it is preferable to design the concavo-convex structure based on the light having the shortest wavelength among the light emitted from the light source. Hereinafter, the shortest wavelength among the light emitted from the light source is referred to as a reference wavelength. For example, since the i-line has a wavelength distribution of 365 nm ± 10 nm, the reference wavelength is 355 nm, and it is preferable to design based on the reference wavelength. Since the g-line has a wavelength distribution of 436 nm ± 5 nm, the reference wavelength is 431 nm, and it is preferable to design around the reference wavelength. When the pitch, which is the distance between adjacent convex parts (or concave parts) of the concavo-convex structure, is 0.7 times or less than the reference wavelength, the above-described improvement in transmittance and reduction in incident angle dependency are realized. This is preferable because it is possible. The lower limit of the pitch is preferably 50 nm because the dust-proof film has good peelability and productivity can be maintained. The height of the convex part is preferably 2 or less in aspect ratio (the length of the convex part top part / the length of the convex part bottom part in the surface of the dustproof film 20) because the peelability of the dustproof film is good. The lower limit is preferably 30 nm or more because the above optical performance can be expressed. In order to further exhibit the above optical performance, the filling rate (occupied area of the concavo-convex structure) is preferably 70% or more, more preferably 85% or more, and particularly preferably 95% or more. .

  When the dust-proof film 20 is used as a liquid-crystal dust-proof film, the light emitted from the light source has a peak top in the visible light region (300 nm to 800 nm). Therefore, the liquid-crystal dust-proof film has excellent transmittance in this wavelength region. It is required to have. When it is desired to suppress the reflectance in the visible light region and increase the transmittance, the adjacent distance between the convex portions is preferably 150 nm to 500 nm, more preferably 150 nm to 200 nm, and the preferred convex height is 1 nm to 5000 nm, More preferably, it is 100 nm or more and 500 nm or less. These convex-shaped filling structures may be hexagonal close packed, square lattice, or random.

  When the dustproof film 20 is used as a dustproof film for ArF, the light emitted from the light source has a peak top at 193 nm. Therefore, the dustproof film for ArF has excellent transmittance at this wavelength and the incident angle of the transmittance. Small dependency is required. When it is desired to suppress the reflectance at 193 nm and increase the transmittance, the adjacent distance between the convex portions is preferably 10 nm to 500 nm, more preferably 50 nm to 200 nm, and the preferred convex height is 1 nm to 1000 nm, more preferably. Is from 50 nm to 500 nm. Furthermore, the surface fine uneven shape not only provides an antireflection function and excellent transmission characteristics, but also improves the effect of suppressing foreign matter adhesion.

  The fine concavo-convex structure of the dustproof film 20 is a pillar shape including a plurality of conical, pyramidal, or elliptical cone-shaped convex portions, or a hole shape including a plurality of conical, pyramidal, or elliptical conical concave portions, and is adjacent to the dust-proof film 20. It is preferable that the distance between the projecting parts is 1 nm or more and 1000 nm or less, and the height of the projecting parts is 1 nm or more and 1000 nm or less. With this configuration, the incidence angle dependency is small, and excellent transmittance can be obtained in a wide wavelength region.

(E) Antireflection film laminating step The antireflection film 21 may be provided on the surface of the dustproof film 20 on which the concavo-convex structure is formed, or may be provided on the surface opposite to the surface of the dustproof film 20 provided with the fine concavo-convex structure. . The antireflection film 21 may be a single layer or multiple layers. Examples of the material for the antireflection film 21 include tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene ternary copolymer and a fluororesin having a perfluoroalkyl ether ring structure (in particular, Teflon AF (registered trademark) manufactured by Du Pont). ), Cytop (trade name) manufactured by Asahi Glass Co., Algoflon (trade name) manufactured by Augmont, and polyfluoroacrylate are preferred.), And materials having a low refractive index such as calcium fluoride, magnesium fluoride, and barium fluoride. Can be preferably used. The method for producing the antireflection layer is not particularly limited, such as spin coating, roll coating, knife coating, casting, vapor deposition, sputtering, etc. preferable.

  As described above, in the method for producing a dustproof film according to the present embodiment, the fine uneven structure provided on the outer peripheral surface of the cylindrical mold 104 is continuously transferred to the surface of the cured resin layer 13. Since the resin mold 15 is produced using the reel-shaped resin mold 12, it is not necessary to use an exposure interference method or an electron beam drawing method for producing the resin mold 15. Thereby, since the large area resin mold 15 used for manufacturing the dustproof film 20 can be easily produced, the large area dustproof film 20 can be produced with high productivity. In particular, since the dust-proof film 20 having a fine concave-convex structure with a large area such as a meter angle can be produced, it can be used as a dust-proof film not only for semiconductors but also for liquid crystal displays.

  Further, in the method for producing a dustproof film according to the above-described embodiment, the resin mold has a fluorine element concentration (Es) in the surface portion on the fine concavo-convex structure surface side and an average fluorine concentration (Eb) in the resin layer described above. Since Expression (1) is satisfied, a concentration gradient is formed from one surface side of the resin mold toward the other surface side. This concentration gradient causes the fluorine concentration in the surface portion on the fine concavo-convex structure side to be relatively higher than the average fluorine concentration (Eb) in the resin, so that the dust-proof film provided on the surface on the fine concavo-convex structure side from the resin mold Peeling is easy. Thereby, even when a dustproof film having a fine relief structure is provided over a large area, the dustproof film can be peeled from the resin mold without damaging the fine relief structure. As a result, it is possible to realize a method for manufacturing a dustproof film that is difficult to adhere to foreign matter, has excellent antireflection performance and transmittance over a wide wavelength region, and has a high productivity that provides a dustproof film capable of increasing the area.

<Example 1>
(A) Mold production process A quartz glass roll was used as a substrate of a cylindrical mold. A fine concavo-convex structure was formed on the outer peripheral surface of the quartz glass roll by a direct drawing lithography method using a semiconductor laser on the outer peripheral surface of the quartz glass roll. OPTOOL HD-1100Z (manufactured by Daikin Chemical Industries, Ltd.) was applied to the outer peripheral surface of the quartz glass roll having a fine concavo-convex structure, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours and fixed. Then, it wash | cleaned 3 times by OPTOOL HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented.

  As the substrate (transparent sheet), PET film: A4100 (manufactured by Toyobo: width 300 mm, thickness 100 μm) was used. As a photocurable resin, OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350) and Irgacure 184 (manufactured by Ciba) are in a ratio of 15: 100: 5.5 by weight. And a mixture of a photo-curing resin was used. This photocurable resin was applied to the surface of the base material (the easy-adhesion surface of the PET film) by microgravure coating (manufactured by Yasui Seiki Co., Ltd.) so as to have a coating film thickness of 6 μm.

Next, the base material (PET film) coated with the photocurable resin was pressed against the cylindrical mold with a nip roll (0.1 MPa), and the temperature was 20 ° C., the humidity was 50%, and the center of the lamp. Ultraviolet rays are irradiated using a UV exposure device (H-bulb manufactured by Fusion UV Systems Japan Co., Ltd.) so that the integrated exposure amount is 600 mJ / cm ^2. A reel-shaped resin mold (length: 200 m, width: 300 mm) was transferred. As a result of confirming the surface unevenness of the surface of the reel-shaped resin mold with a scanning electron microscope, the adjacent distance between the protrusions was 250 nm, and the height of the protrusions was 250 nm.

(B) Resin mold manufacturing process As the inorganic substrate, an 8-inch silicon wafer was used. The silicon wafer was subjected to ozone treatment for 15 minutes before use.

・ Resin mold 1
A solution in which propylene glycol monomethyl ether solvent was added three times to the same resin as the resin from which the resin mold was produced was prepared. This solution was spin-coated on a silicon wafer, then allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 1 minute (laminate 1).

  A resin mold was bonded to the laminate 1, and then pressed in a state where both surfaces were sandwiched between rubber. The pressurization was performed at 0.05 MPa for 10 minutes. After pressurization, UV light was irradiated from the resin mold side, followed by heating at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold. The resin mold was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the shape of the surface fine irregularities of the obtained resin mold by observation with a scanning electron microscope, the adjacent distance between the concave portions was 250 nm, and the height of the concave portions was 250 nm.

・ Resin mold 2
5 parts by mass of I.184 (Irgacure 184 Ciba) was added to 100 parts by mass of 3APTMS (3acryloxypropyltrimethoxysilane, KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was stirred at room temperature for 15 minutes. Subsequently, the resultant was diluted 10 times with a methyl ethyl ketone solvent and formed on a silicon wafer subjected to ozone treatment by spin coating. After film formation, the mixture was allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 10 minutes (laminate 1).

  Then, the solution which added the propylene glycol monomethyl ether solvent 3 times with respect to resin similar to resin which produced the resin mold was prepared. This solution was spin-coated on the film-forming surface of the laminate 1, and then allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 1 minute (laminate 2).

  A resin mold was bonded to the laminate 2, and then pressed in a state where both surfaces were sandwiched with rubber. Pressurization was performed at 0.05 MP for 10 minutes. After pressurization, UV light was irradiated from the resin mold side, followed by heating at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold. The resin mold was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the shape of the surface fine irregularities of the obtained resin mold by observation with a scanning electron microscope, the adjacent distance between the concave portions was 250 nm, and the height of the concave portions was 250 nm. XPS analysis was performed on each resin mold surface to derive the Es value, and the Eb value was derived from the charged amount. The Es / Eb values on the surface of the obtained resin mold were 38 for the resin mold 1 and 37 for the resin mold 2.

(C) Dust-proof film layer forming step A polymer solution was prepared by dissolving cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Company, yield strain about 4%, tensile elongation about 15%) in ethyl lactate. This solution was cast on the fine concavo-convex structure surface of each resin mold and stretched to form a film by spin coating. A dust-proof film layer was formed on the resin mold by drying on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each.

(D) Dust-proof film material layer peeling step Subsequently, the film was dried at 80 ° C. for 5 minutes, and then dried at 180 ° C. for 5 minutes. After returning to room temperature, the dust-proof film was peeled off by pressing and separating the frame with the adhesive. When the surface of the dust-proof film was observed with an atomic force microscope, the adjacent distance between the convex portions was 250 nm, and the convex portion height was 250 nm. The transmittance (365 nm, 436 nm), film thickness, and area of the obtained dustproof film are shown in Table 1 below.

<Example 2>
(A) Mold production process A quartz glass roll was used as a substrate of a cylindrical mold. A fine concavo-convex structure was formed on the surface of the quartz glass by a direct drawing lithography method using a semiconductor laser on the outer peripheral surface of the quartz glass roll. OPTOOL HD-1100Z (manufactured by Daikin Chemical Industries, Ltd.) was applied to the surface of the quartz glass roll on which the fine concavo-convex structure was formed, 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 OPTOOL HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented.

  As the substrate (transparent sheet), PET film: A4100 (manufactured by Toyobo: width 300 mm, thickness 100 μm) was used. As a photocurable resin, OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd. M350) and Irgacure 184 (manufactured by Ciba) are in a ratio of 15: 100: 5.5 by weight. And a mixture of a photo-curing resin was used. This photocurable resin was applied to the surface of the base material (the easy-adhesion surface of the PET film) by microgravure coating (manufactured by Yasui Seiki Co., Ltd.) so as to have a coating film thickness of 6 μm.

Next, the base material (PET film) coated with the photocurable resin was pressed against the cylindrical mold with a nip roll (0.1 MPa), and the temperature was 20 ° C., the humidity was 50%, and the center of the lamp. Ultraviolet rays are irradiated using a UV exposure device (H-bulb manufactured by Fusion UV Systems Japan Co., Ltd.) so that the integrated exposure amount is 600 mJ / cm ^2. A reel-shaped resin mold (length: 200 m, width: 300 mm) was transferred. As a result of confirming the surface unevenness of the surface of the reel-shaped resin mold with a scanning electron microscope, the adjacent distance between the protrusions was 250 nm, and the height of the protrusions was 250 nm.

(B) Resin mold manufacturing process As the inorganic substrate, an 8-inch silicon wafer was used. The silicon wafer was subjected to ozone treatment for 15 minutes before use.

・ Resin mold 1
A solution in which propylene glycol monomethyl ether solvent was added three times to the same resin as the resin from which the resin mold was produced was prepared. This solution was spin-coated on a silicon wafer, then allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 1 minute (laminate 1).

  A resin mold was bonded to the laminate 1, and then pressed in a state where both surfaces were sandwiched between rubber. Pressurization was performed at 0.05 MP for 10 minutes. After pressurization, UV light was irradiated from the resin mold side, followed by heating at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold. The resin mold was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the shape of the surface fine irregularities of the obtained resin mold by observation with a scanning electron microscope, the adjacent distance between the concave portions was 250 nm, and the height of the concave portions was 250 nm.

・ Resin mold 2
5 parts by mass of I.184 (Irgacure 184 Ciba) was added to 100 parts by mass of 3APTMS (3acryloxypropyltrimethoxysilane, KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was stirred at room temperature for 15 minutes. Subsequently, the resultant was diluted 10 times with a methyl ethyl ketone solvent and formed on a silicon wafer subjected to ozone treatment by spin coating. After film formation, the mixture was allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 10 minutes (laminate 1).

  Then, the solution which added the propylene glycol monomethyl ether solvent 3 times with respect to resin similar to resin which produced the resin mold was prepared. This solution was spin-coated on the film-forming surface of the laminate 1, and then allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 1 minute (laminate 2).

  A resin mold was bonded to the laminate 2, and then pressed in a state where both surfaces were sandwiched with rubber. Pressurization was performed at 0.05 MP for 10 minutes. After pressurization, UV light was irradiated from the resin mold side, followed by heating at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold. The resin mold was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the shape of the surface fine irregularities of the obtained resin mold by observation with a scanning electron microscope, the adjacent distance between the concave portions was 250 nm, and the height of the concave portions was 250 nm. XPS analysis was performed on each resin mold surface to derive the Es value, and the Eb value was derived from the charged amount. The Es / Eb values on the surface of the obtained resin mold were 38 for the resin mold 1 and 37 for the resin mold 2.

(C) Dust-proof film layer forming step A polymer solution was prepared by dissolving cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Company, yield strain about 4%, tensile elongation about 15%) in ethyl lactate. This solution was cast on the fine concavo-convex structure surface of each resin mold and stretched to form a film by spin coating. A dust-proof film layer was formed on the resin mold by drying on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each.

(E) Antireflection film laminating step Further, perfluorotributylamine (Fluorinert FC) was added so that CYTOP CTX-809SP2 (manufactured by Asahi Glass Co., Ltd.) was 2.0% with a solvent on the dustproof film layer on each of the above resin molds. The solution diluted with −43 (manufactured by Sumitomo 3M) was cast and stretched to form a film by spin coating.

(D) Dust-proof film material layer peeling step Subsequently, the film was dried at 80 ° C. for 5 minutes, and then dried at 180 ° C. for 5 minutes. After returning to room temperature, the dust-proof film was peeled off by pressing and separating the frame with the adhesive. When the cellulose acetate propionate (dust-proof film side) surface of the peeled dust-proof film was observed with an atomic force microscope, the adjacent distance between the convex parts was 250 nm and the convex part height was 250 nm. The transmittance (365 nm, 436 nm), film thickness, and area of the obtained dustproof film with antireflection film are shown in Table 1 below.

(Comparative example)
(B) Resin mold manufacturing process As the inorganic substrate, an 8-inch silicon wafer (silicon substrate) was used. This silicon substrate was used as a mold.

(C) Dust-proof film layer forming step A polymer solution was prepared by dissolving cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Company, yield strain about 4%, tensile elongation about 15%) in ethyl lactate. This solution was cast on a silicon substrate and stretched to form a film by spin coating. A dust-proof film layer was formed on the silicon substrate by drying for 5 minutes each on a hot plate at 80 ° C. and 180 ° C.

(D) Dust-proof film material layer peeling step Subsequently, the film was dried at 80 ° C. for 5 minutes, and then dried at 180 ° C. for 5 minutes. After returning to room temperature, the dust-proof film was peeled off by pressing and separating the frame with the adhesive. The transmittance (365 nm, 436 nm), film thickness, and area of the obtained dustproof film are shown in Table 1 below.

  As can be seen from Table 1, in Example 1 and Example 2 using the resin mold satisfying 20 ≦ Es / Eb ≦ 200, it is understood that a large area dust-proof film having excellent transmittance can be obtained. As a result, when the fluorine element concentration (Es / Eb) of the resin mold is within a predetermined range, a concentration gradient of the fluorine element concentration is generated in the resin mold, and this concentration gradient causes the resin mold 1 and the resin mold 2 to have a concentration gradient. This is thought to be due to the improved peelability of the dust-proof film. Further, as can be seen from Example 2, it can be seen that a dust-proof film excellent in transmittance can be obtained by laminating an anti-reflection film on the dust-proof film. On the other hand, it can be seen that the transmittance of the dust-proof film decreases in the comparative example using silicon having a fluorine element concentration (Es / Eb) outside the predetermined range as a mold.

  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 effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

  The present invention makes it possible to obtain a dustproof film that is difficult to adhere to foreign matter, has an antireflection performance and excellent transmittance over a wide wavelength region, and can be increased in area and has high productivity. The method can be realized, and can be suitably used as a dust-proof film for semiconductors and liquid crystal displays.

DESCRIPTION OF SYMBOLS 11 Base material 12 Reel-shaped resin mold 13,17 Uncured resin layer 14,18 Cured resin layer 15 Resin mold 16 Inorganic substrate 19 Uncured dustproof film material layer 20 Dustproof film 21 Antireflection film 22 Adhesive layer 101 Original fabric roll 102 Winding Take-up roll 103 Coating device 104 Cylindrical mold 105 Pressure means 106 Light source 107 Drying furnace

Claims (3)

A mold preparation step for preparing a resin mold provided with a base material and a cured resin layer provided on the base material and having a fine uneven structure on the surface;
In a state where the fine concavo-convex structure forming surface of the resin mold is bonded to the uncured resin layer provided on the inorganic substrate, the uncured resin layer is cured to form a cured resin layer, and then the cured resin from the resin mold. A resin mold preparation step of peeling off a layer and preparing a resin mold provided with the cured resin layer provided on the surface of the inorganic substrate and the fine uneven structure of the resin mold provided on the inorganic substrate;
An uncured dustproof film material layer forming step of forming an uncured dustproof film material layer on the cured resin layer of the resin mold;
A dust-proof film peeling step of curing the uncured dust-proof film material layer to form a dust-proof film and then peeling the dust-proof film from the resin mold to produce a dust-proof film,
The ratio of the fluorine element concentration (Es) in the surface portion of the cured resin layer on the fine concavo-convex structure forming surface side of the resin mold to the average fluorine concentration (Eb) in the cured resin layer satisfies the following formula (1). A method for producing a dust-proof film.
Formula (1)
20 ≦ Es / Eb ≦ 200   The antireflection film laminating step of laminating an antireflection film layer on the dustproof film material layer is included between the dustproof film material layer forming step and the dustproof film peeling step. Manufacturing method of dustproof film.   The fine concavo-convex structure of the dust-proof film is a pillar shape including a plurality of conical, pyramidal, or elliptical cone-shaped convex portions, or a hole shape including a plurality of conical, pyramidal, or elliptical conical concave portions, The method for producing a dustproof film according to claim 1 or 2, wherein the distance between adjacent convex portions is 1 nm or more and 1000 nm or less, and the height of the convex portions is 1 nm or more and 1000 nm or less.

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