WO2017057220A1 - Water-repellent member and method for manufacturing same - Google Patents

Water-repellent member and method for manufacturing same Download PDF

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Publication number
WO2017057220A1
WO2017057220A1 PCT/JP2016/078163 JP2016078163W WO2017057220A1 WO 2017057220 A1 WO2017057220 A1 WO 2017057220A1 JP 2016078163 W JP2016078163 W JP 2016078163W WO 2017057220 A1 WO2017057220 A1 WO 2017057220A1
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Prior art keywords
water
columnar
repellent member
resin layer
fluorine
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PCT/JP2016/078163
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French (fr)
Japanese (ja)
Inventor
孝徳 高橋
目黒　晃
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綜研化学株式会社
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Publication of WO2017057220A1 publication Critical patent/WO2017057220A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials

Definitions

  • the present invention relates to a water repellent member and a method for producing the same.
  • Patent Documents 1 and 2 disclose a water-repellent member obtained by imparting an uneven shape to a resin using an imprint technique.
  • the contact angle of the water repellent members produced in the examples of Patent Documents 1 and 2 is in the range of 150 to 163 °, and the water repellency is insufficient depending on the intended use.
  • the present invention has been made in view of such circumstances, and provides a water-repellent member having extremely excellent water repellency.
  • a base material and a resin layer are provided on at least one surface of the base material, the resin layer has a plurality of columnar convex portions, and the columnar convex portions are:
  • a cross-sectional area of 400 ⁇ to 2500 ⁇ nm 2 a pitch at which the columnar protrusions are formed is 90 to 400 nm, a gap between two adjacent columnar protrusions is 50 to 360 nm, and fluorine atoms containing fluorine atoms
  • a water repellent member is provided in which a containing layer is provided so as to cover the columnar protrusions.
  • the present inventor formed a columnar convex portion having a specific cross-sectional area and pitch on a resin layer formed on a base material, and when fluorine atoms were present on the surface thereof, a water repellent member having excellent water repellency. And the present invention has been completed.
  • the fluorine atom-containing layer includes a fluorine-containing group.
  • an inorganic film is provided between the columnar convex portion and the fluorine atom-containing layer.
  • the fluorine-containing group is a perfluoroalkyl group.
  • the columnar convex portion has a cross-sectional area of 900 ⁇ to 2500 ⁇ nm 2 .
  • the columnar convex portion has a columnar shape.
  • the columnar convex portion has a height of 50 to 400 nm.
  • the columnar convex portion has a height of 150 to 400 nm.
  • the resin layer is made of (meth) acrylic resin.
  • the contact angle with respect to water is 170 degrees or more.
  • an inorganic film is formed so that a plurality of columnar protrusions are formed on a transferred resin layer formed by applying a photocurable resin composition on a substrate, and the columnar protrusions are covered.
  • a method for producing a water-repellent member comprising forming a fluorine atom-containing layer so as to cover the inorganic film by reacting the inorganic film with a fluorine-containing silane coupling agent.
  • the columnar protrusion is formed by a nanoimprint method using a mold.
  • the columnar convex portion is formed by forming a base columnar convex portion by a nanoimprint method using a mold and then performing oxygen plasma ashing to reduce the base columnar convex portion.
  • a photocurable resin composition is applied on a substrate to form a transferred resin layer, and the transferred resin layer is pressed against the transferred resin layer.
  • a step of forming a plurality of columnar convex portions by irradiating active energy rays to the resin layer to be transferred, and the resin layer to be transferred is formed using a resin containing a reactive fluorine additive
  • a method for producing a water repellent member is provided.
  • FIG. 1 shows a water-repellent member 1 according to an embodiment of the present invention, in which (a) is a plan view and (b) is a cross-sectional view along AA.
  • (A)-(c) shows the manufacturing process of the water-repellent member 1 of one Embodiment of this invention.
  • (A) to (c) show manufacturing steps of the water-repellent member 1 continued from FIG.
  • the water-repellent member 1 of one embodiment of the present invention includes a base 6 and a resin layer 7 on at least one surface of the base 6, and the resin layer 7 has a plurality of columnar protrusions 3.
  • the columnar protrusion 3 has a cross-sectional area of 400 ⁇ to 2500 ⁇ nm 2 , a pitch P at which the columnar protrusion 3 is formed is 90 to 400 nm, and a gap G between two adjacent columnar protrusions 3 is 50 to
  • the fluorine atom-containing layer 9 having a thickness of 360 nm and containing fluorine atoms is provided so as to cover the columnar protrusions 3.
  • An inorganic film 8 may be provided between the columnar protrusion 3 and the fluorine atom-containing layer 9.
  • the columnar convex portion 3 covered with the fluorine atom-containing layer 9 is referred to as a coated columnar convex portion 5.
  • the form of the water repellent member 1 is not particularly limited, but is preferably a flexible water repellent film.
  • the contact angle with respect to the water of the water repellent member 1 is not specifically limited, 170 degree
  • the material of the base material 6 is not specifically limited, It is preferable that they are transparent base materials, such as a resin base material and a quartz base material, and it is more preferable that it is a resin base material from a flexible viewpoint.
  • the resin constituting the resin base material include one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyester, polyolefin, polyimide, polysulfone, polyethersulfone, cyclic polyolefin, and polyethylene naphthalate.
  • the substrate 6 is preferably in the form of a flexible film, and the thickness is preferably in the range of 25 to 500 ⁇ m.
  • the resin constituting the resin layer 7 is not particularly limited.
  • the resin layer 7 is made of a resin such as a (meth) acrylic resin, a styrene resin, an olefin resin, a polycarbonate resin, a polyester resin, an epoxy resin, or a silicone resin. It is preferable to use (meth) acrylic resin for the reason that it is possible to easily adjust the shape of the unevenness.
  • the columnar convex part 3 is a convex part whose cross-sectional area is substantially constant in the height direction.
  • the cross-sectional shape of the columnar convex portion 3 is preferably a circle, but may be another shape such as an ellipse, an ellipse, or a polygon (such as a square, a rectangle, or a regular hexagon).
  • the diameter is preferably 40 to 100 nm, and more preferably 60 to 100 nm.
  • This diameter is specifically, for example, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 nm, and between any two of the numerical values exemplified here It may be within the range.
  • the cross-sectional area when the diameter is 40 nm is 400 ⁇ nm 2
  • the cross-sectional area when the diameter is 100 nm is 2500 ⁇ nm 2 .
  • the columnar convex portion 3 preferably has the same cross-sectional area as that of a circle.
  • the columnar convex portion 3 preferably has a cross-sectional area of 400 ⁇ to 2500 ⁇ nm 2 and more preferably 900 ⁇ to 2500 ⁇ nm 2 regardless of the cross-sectional shape.
  • this cross-sectional area is, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300. 2400 and 2500 ⁇ nm 2 , and may be within a range between any two of the numerical values exemplified here.
  • the pitch P at which the columnar protrusions 3 are formed is 90 to 400 nm, and the gap G between two adjacent columnar protrusions 3 is 50 to 360 nm.
  • the pitch P is too small or the gap G is too small, the interval between the adjacent columnar convex portions 3 becomes too narrow and the water repellency is hardly increased. Further, if the pitch P is too large, a structural color is expressed by the columnar convex portions 3 and transparency is easily impaired.
  • the pitch P is, for example, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 nm, and may be within a range between any two of the numerical values exemplified here.
  • the gap G is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360 nm, and may be within a range between any two of the numerical values exemplified here.
  • the height of the columnar protrusion 3 is not particularly limited, but is, for example, 50 to 400 nm, and preferably 150 to 400 nm. This is because if the height of the columnar convex portion 3 is too low, the water repellency is hardly increased, and if the height of the columnar convex portion 3 is too high, the columnar convex portion 3 is likely to collapse. Specifically, the height of the columnar convex portion 3 is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220.
  • a fluorine atom-containing layer 9 is provided so as to cover the columnar protrusion 3.
  • the fluorine atom-containing layer 9 only needs to contain fluorine atoms, and its thickness and configuration are not limited. By providing the fluorine atom-containing layer 9, the water repellency is enhanced.
  • the fluorine atom-containing layer 9 preferably contains a fluorine-containing group.
  • the fluorine-containing group is a perfluoroalkyl group, and more specifically, a perfluoroalkylsilane group.
  • the carbon number of the perfluoroalkyl group is, for example, 1 to 10, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the numerical values exemplified here are It may be within a range between any two.
  • the fluorine-containing group is preferably chemically bonded to the columnar protrusion 3 or the inorganic film 8.
  • the inorganic film 8 has high adhesion to the resin layer 7, and the fluorine-containing group tends to form a strong chemical bond to the inorganic film 8, so that the columnar convex portion 3 and the fluorine atom-containing layer 9 are interposed.
  • the fluorine atom-containing layer 9 is firmly held on the columnar protrusion 3.
  • Examples of the inorganic film 8 include an inorganic oxide film, an inorganic nitride film, and an inorganic oxynitride film.
  • Examples of inorganic elements constituting the inorganic film 8 include Si and Al.
  • the inorganic film 8 is, for example, a silicon oxide film or an aluminum oxide film.
  • the thickness of the inorganic film 8 is not particularly limited, but is, for example, 1 to 20 nm.
  • the fluorine atom-containing layer 9 can be formed by forming the inorganic film 8 on the columnar convex portion 3 and reacting the inorganic film 8 with the fluorine-containing silane coupling agent.
  • the fluorine-containing silane coupling agent is, for example, perfluoroalkyltrialkoxy (methoxy, ethoxy, etc.) silane. Even if a fluorine-containing silane coupling agent is allowed to act on the columnar convex portion 3 without forming the inorganic film 8, it is difficult to form a strong chemical bond. Therefore, it is preferable to form the inorganic film 8 on the columnar convex portion 3 in advance.
  • Examples of the fluorine-containing silane coupling agent include OPTOOL DSX (manufactured by Daikin Industries).
  • the manufacturing method of the water-repellent member of one embodiment of the present invention includes a transferred resin layer forming step, a columnar convex portion forming step, an inorganic film forming step, and a fluorine atom-containing layer forming step.
  • a transferred resin layer forming step a columnar convex portion forming step
  • an inorganic film forming step a fluorine atom-containing layer forming step.
  • a photocurable resin composition is applied on a substrate 6 to form a transferred resin layer 11.
  • the details of the substrate 6 are as described above.
  • the photocurable resin composition contains a monomer and a photoinitiator and has a property of being cured by irradiation with active energy rays.
  • Active energy rays is a general term for energy rays that can cure a photocurable resin composition, such as UV light, visible light, and electron beams.
  • Monomers include photopolymerizable monomers for forming (meth) acrylic resins, styrene resins, olefin resins, polycarbonate resins, polyester resins, epoxy resins, silicone resins, etc., and photopolymerizable (meth) acrylic.
  • System monomers are preferred.
  • (meth) acryl means methacryl and / or acryl
  • (meth) acrylate means methacrylate and / or acrylate.
  • the photoinitiator is a component added to promote the polymerization of the monomer, and is preferably contained in an amount of 0.1 part by mass or more with respect to 100 parts by mass of the monomer.
  • the upper limit of content of a photoinitiator is not prescribed
  • the photocurable resin composition is a range in which components such as a solvent, a polymerization inhibitor, a chain transfer agent, an antioxidant, a photosensitizer, a filler, and a leveling agent do not affect the properties of the photocurable resin composition. May be included.
  • the photocurable resin composition can be produced by mixing the above components by a known method.
  • the photocurable resin composition can be applied on the substrate 6 by a method such as spin coating, spray coating, bar coating, dip coating, die coating, and slit coating to form the transferred resin layer 11.
  • the resin layer 7 having the base columnar convex portions 4 is formed by curing the transferred resin layer 11 by irradiating the active energy rays 17 to the substrate 11. That is, the base columnar convex portion 4 is formed by the nanoimprint method using the mold 13.
  • the base columnar protrusion 4 is formed to have a size larger than the desired columnar protrusion 3.
  • the type of the mold 13 is not particularly limited.
  • a resin mold, a nickel mold, or the like can be used.
  • the pressure for pressing the mold 13 against the transferred resin layer 11 may be any pressure that can transfer the shape of the reversal pattern 15 to the transferred resin layer 11.
  • the active energy ray 17 applied to the transferred resin layer 11 may be irradiated with an integrated light amount sufficient to sufficiently cure the transferred resin layer 11, and the integrated light amount is, for example, 100 to 10,000 mJ / cm 2 .
  • the transferred resin layer 11 is cured by irradiation with the active energy ray 17.
  • the active energy rays 17 are irradiated from the substrate 6 side, but the active energy rays 17 may be irradiated from the mold side.
  • the uncured photocurable resin composition may be washed away with a solvent.
  • an oxygen plasma ashing process is performed to reduce the base columnar protrusions 4 to form the columnar protrusions 3.
  • the conditions for the oxygen plasma ashing treatment can be set as appropriate to obtain the columnar convex portions 4 having a desired shape.
  • the columnar convex part 4 of desired shape is obtained by reducing the size of the base columnar convex part 4 by the oxygen plasma ashing process after forming the base columnar convex part 4 by the nanoimprint method.
  • various water repellent members having different columnar convex portions 3 can be obtained.
  • the columnar convex portion 3 may be directly formed by the nanoimprint method using the mold 13 having the reverse pattern 15 of the columnar convex portion 3. In this case, the oxygen plasma ashing process can be omitted.
  • the transferred resin layer 11 may be formed using a resin containing a reactive fluorine additive.
  • a reactive fluorine additive is a compound comprising a light (eg, UV) reactive group and a fluorine-containing group.
  • the fluorine-containing group 9 is formed so that the fluorine-containing group is exposed on the surface of the resin layer 7 and covers the columnar protrusions 3. Therefore, in this case, excellent water repellency is exhibited without separately forming the fluorine atom-containing layer 9.
  • the reactive fluorine additive Megafac RS series (manufactured by DIC) may be mentioned.
  • an inorganic film 8 is formed so as to cover the columnar protrusions 3.
  • the inorganic film 8 can be formed by a method such as vapor deposition or sputtering.
  • the inorganic film 8 covers both the upper surface and the side surface of the columnar convex portion 3, but the inorganic film 8 may be formed so as to cover at least a part of the columnar convex portion 3, For example, you may form so that only the upper surface of the columnar convex part 3 may be covered.
  • the inorganic film 8 is formed so as to cover the entire surface of the resin layer 7, but may be formed so as to cover only the columnar convex portions 3.
  • a fluorine atom-containing layer 9 is formed so as to cover the inorganic film 8 by reacting the inorganic film 8 with a fluorine-containing silane coupling agent.
  • the fluorine atom-containing layer 9 covers both the upper surface and the side surface of the columnar convex portion 3, but the fluorine atom-containing layer 9 is formed so as to cover at least a part of the columnar convex portion 3. For example, you may form so that only the upper surface of the columnar convex part 3 may be covered.
  • the fluorine atom-containing layer 9 is formed so as to cover the entire surface of the resin layer 7, but may be formed so as to cover only the columnar protrusions 3.
  • the inorganic film 8 is present between the fluorine atom-containing layer 9 and the resin layer 7 in any region, but in some regions, the fluorine atom-containing layer 9 and the resin are present.
  • the layer 7 may be in direct contact.
  • the water-repellent member of the present invention is a window, lens, display, sensor, etc. used for transportation equipment, buildings and communication equipment, as well as articles that require dew condensation prevention (air conditioning equipment, heat exchangers, condensers, etc.), ventilation fans, It can be suitably used for actuators, fuel cell electrodes, nozzles, filters, waterproof construction sheets, decorative boards, road installations (traffic signs, traffic lights, soundproof walls, traffic guide boards, blinker lights), and the like.
  • Samples 3 to 4 and 9 are examples of the present invention, and the remaining samples are comparative examples.
  • Multifunctional acrylate monomer Biscoat # 360 (manufactured by Osaka Organic Chemical Industry) 50 parts by mass Biscoat # 700HV (manufactured by Osaka Organic Chemical Industry) 20 parts by mass Biscoat # 310HP (manufactured by Osaka Organic Chemical Industry) 30 parts by mass Photoinitiator Irgacure 184 (manufactured by BASF Japan) 5 parts by mass
  • sample 1 The UV curable resin prepared above was applied to a PET substrate with a bar coater to a thickness of 5 ⁇ m, and applied to a nanohole mold (period 240 nm, diameter 140 nm, depth 250 nm). Lamination was performed with a roller from above so that the surface was pressed against the mold. Thereafter, UV irradiation was performed from the PET substrate side with an integrated light amount of 500 mJ / cm 2 to cure the UV curable resin. The mold and the resin-cured PET base material were peeled off to produce a nanopillar transfer product having the inverted shape of the mold.
  • SiO 2 is deposited on the shaped surface under conditions of a beam voltage of 500 [V], a beam current of 400 [mA], and a film forming pressure of 1 [Pa]. Then, a thin film of SiO 2 was coated. Then, a fluorine-containing silane coupling agent (Daikin Kogyo Co., Ltd., OPTOOL DSX) is applied to the surface, reacted under conditions of a temperature of 50 ° C. and a humidity of 80%, and the surface is fluorinated so that the fluorine atom-containing layer A water-repellent film (Sample 1) was formed.
  • a fluorine-containing silane coupling agent (Daikin Kogyo Co., Ltd., OPTOOL DSX) is applied to the surface, reacted under conditions of a temperature of 50 ° C. and a humidity of 80%, and the surface is fluorinated so that the fluorine atom-containing layer A water-repellent film (
  • Examples 5-8 Water-repellent films (samples 5 to 8) were prepared in the same manner as samples 1 to 4, except that a nanopillar mold (period 240 nm, diameter 160 nm, height 250 nm) was used.
  • Example 9 A mixture obtained by adding 10 parts of the reactive fluorine additive (manufactured by DIC, Megaface RS-75) to the above UV curable resin was applied to a PET substrate with a bar coater so as to have a thickness of 5 ⁇ m. Lamination was performed so that the resin surface was pressed against a nanohole-shaped (period 240 nm, diameter 60 nm, depth 250 nm) mold. Thereafter, UV irradiation was performed from the PET base material side with an integrated light amount of 1000 mJ / cm 2 to cure, and the PET base material was released from the mold to produce the above-mentioned inverted transfer product.
  • the reactive fluorine additive manufactured by DIC, Megaface RS-75
  • a water-repellent film in which a fluorine-containing silane coupling agent (manufactured by Daikin Industries, Optool DSX) was applied to the produced transfer product and the surface was subjected to fluorine treatment to form a fluorine atom-containing layer (Sample 9) was made.
  • a fluorine-containing silane coupling agent manufactured by Daikin Industries, Optool DSX
  • Examples 10 to 11 Water-repellent films (Samples 10 to 11) were produced in the same manner as Sample 1, except that a mold having a moth-eye-shaped reversal pattern was used.
  • Sample 12 was subjected to oxygen plasma ashing treatment on the water repellent film of Sample 11 in the same manner as Samples 2-4.
  • ⁇ Diameter, period, height measurement> A part of the sample was excised, the shape was observed using a scanning electron microscope (manufactured by JEOL Ltd., model: JSM-7800F), and measurement was performed using software (PC-SUM) attached to the microscope. In addition, the diameter was measured according to the center part of height.
  • Table 1 shows the details of the shape of each sample and the water contact angle measurement results.
  • the water-repellent films of Samples 3, 4 and 9 as examples of the present invention were very excellent in water repellency, but the water-repellent films of the remaining samples were more than the samples of Examples. The water repellency was poor.
  • 1 water-repellent member
  • 3 columnar convex portion
  • 4 base columnar convex portion
  • 5 coated columnar convex portion
  • 6 base material
  • 7 resin layer
  • 8 inorganic film
  • 9 fluorine atom-containing layer
  • 11 Transferred resin layer
  • 13 mold
  • 15 reverse pattern
  • 17 active energy ray

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Abstract

Provided is a water-repellent member having extremely excellent water repellency. Through the present invention, there is provided a water-repellent member provided with a substrate and a resin layer on at least one surface of the substrate, the resin layer having a plurality of columnar projections, the columnar projections having a cross-sectional area of 400π-2500π nm2, the pitch at which the columnar projections are formed being 90-400 nm, a gap between two adjacent columnar projections being 50-360 nm, and a fluorine-atom-containing layer including fluorine atoms being provided so as to cover the columnar projections.

Description

撥水性部材及びその製造方法Water repellent member and manufacturing method thereof
　本発明は、撥水性部材及びその製造方法に関する。 The present invention relates to a water repellent member and a method for producing the same.
　特許文献１～２には、インプリント技術を用いて樹脂に凹凸形状を付与させた撥水性部材が開示されている。 Patent Documents 1 and 2 disclose a water-repellent member obtained by imparting an uneven shape to a resin using an imprint technique.
特許第５６３０１０４号Patent No. 5630104 特許第５６２６４４１号Patent No. 5626441
　しかし、特許文献１～２の実施例で作製されている撥水性部材の接触角は１５０～１６３°の範囲であり、使用用途によっては、撥水性が不足している。 However, the contact angle of the water repellent members produced in the examples of Patent Documents 1 and 2 is in the range of 150 to 163 °, and the water repellency is insufficient depending on the intended use.
　本発明はこのような事情に鑑みてなされたものであり、撥水性が非常に優れた撥水性部材を提供するものである。 The present invention has been made in view of such circumstances, and provides a water-repellent member having extremely excellent water repellency.
　本発明によれば、本発明によれば、基材と、前記基材の少なくとも一方の面に樹脂層を備え、前記樹脂層は、複数の柱状凸部を有し、前記柱状凸部は、断面積が４００π～２５００πｎｍ２であり、前記柱状凸部が形成されるピッチが９０～４００ｎｍであり、隣接した２つの柱状凸部の間の隙間が５０～３６０ｎｍであり、フッ素原子を含むフッ素原子含有層が前記柱状凸部を覆うように設けられている、撥水性部材が提供される。 According to the present invention, according to the present invention, a base material and a resin layer are provided on at least one surface of the base material, the resin layer has a plurality of columnar convex portions, and the columnar convex portions are: A cross-sectional area of 400π to 2500πnm 2 , a pitch at which the columnar protrusions are formed is 90 to 400 nm, a gap between two adjacent columnar protrusions is 50 to 360 nm, and fluorine atoms containing fluorine atoms A water repellent member is provided in which a containing layer is provided so as to cover the columnar protrusions.
　本発明者は基材上に形成した樹脂層に、特定の断面積及びピッチを有する柱状凸部を形成し、その表面にフッ素原子を存在させたところ、撥水性が非常に優れた撥水性部材が得られることを見出し、本発明の完成に到った。 The present inventor formed a columnar convex portion having a specific cross-sectional area and pitch on a resin layer formed on a base material, and when fluorine atoms were present on the surface thereof, a water repellent member having excellent water repellency. And the present invention has been completed.
　従来は、特許文献１～２に示すように、撥水性部材に形成する凸部は、先端に向かって断面積が小さくなる形状にすることが技術常識であったが、本発明者はこのような技術常識に反して、柱状の凸部を特定の断面積及びピッチで形成したところ、撥水性が非常に良好になるという驚くべき結果が得られた。 Conventionally, as shown in Patent Documents 1 and 2, it has been common technical knowledge that the convex portion formed on the water-repellent member has a shape in which the cross-sectional area decreases toward the tip. Contrary to the common technical knowledge, when the columnar protrusions were formed with a specific cross-sectional area and pitch, a surprising result was obtained that the water repellency was very good.
　以下、本発明の種々の実施形態を例示する。以下に示す実施形態は、互いに組み合わせ可能である。
　好ましくは、前記フッ素原子含有層は、フッ素含有基を含む。
　好ましくは、前記柱状凸部と前記フッ素原子含有層の間に無機膜を備える。
　好ましくは、前記フッ素含有基は、パーフルオロアルキル基である。
　好ましくは、前記柱状凸部は、断面積が９００π～２５００πｎｍ２である。
　好ましくは、前記柱状凸部は、円柱状である。
　好ましくは、前記柱状凸部は、高さが５０～４００ｎｍである。
　好ましくは、前記柱状凸部は、高さが１５０～４００ｎｍである。
　好ましくは、前記樹脂層は、（メタ）アクリル樹脂からなる。
　好ましくは、水に対する接触角が１７０度以上である。 Hereinafter, various embodiments of the present invention will be exemplified. The embodiments described below can be combined with each other.
Preferably, the fluorine atom-containing layer includes a fluorine-containing group.
Preferably, an inorganic film is provided between the columnar convex portion and the fluorine atom-containing layer.
Preferably, the fluorine-containing group is a perfluoroalkyl group.
Preferably, the columnar convex portion has a cross-sectional area of 900π to 2500πnm 2 .
Preferably, the columnar convex portion has a columnar shape.
Preferably, the columnar convex portion has a height of 50 to 400 nm.
Preferably, the columnar convex portion has a height of 150 to 400 nm.
Preferably, the resin layer is made of (meth) acrylic resin.
Preferably, the contact angle with respect to water is 170 degrees or more.
　本発明の別の観点によれば、基材上に光硬化性樹脂組成物を塗布して形成した被転写樹脂層に複数の柱状凸部を形成し、前記柱状凸部を覆うように無機膜を形成し、前記無機膜とフッ素含有シランカップリング剤を反応させることによって前記無機膜を覆うようにフッ素原子含有層を形成する工程を備える、撥水性部材の製造方法が提供される。
　好ましくは、前記柱状凸部は、モールドを用いてナノインプリント法によって形成される。
　好ましくは、前記柱状凸部は、モールドを用いてナノインプリント法によってベース柱状凸部を形成した後に酸素プラズマアッシング処理を行って前記ベース柱状凸部を縮小させることによって形成される。 According to another aspect of the present invention, an inorganic film is formed so that a plurality of columnar protrusions are formed on a transferred resin layer formed by applying a photocurable resin composition on a substrate, and the columnar protrusions are covered. There is provided a method for producing a water-repellent member, comprising forming a fluorine atom-containing layer so as to cover the inorganic film by reacting the inorganic film with a fluorine-containing silane coupling agent.
Preferably, the columnar protrusion is formed by a nanoimprint method using a mold.
Preferably, the columnar convex portion is formed by forming a base columnar convex portion by a nanoimprint method using a mold and then performing oxygen plasma ashing to reduce the base columnar convex portion.
　本発明のさらに別の観点によれば、基材上に光硬化性樹脂組成物を塗布して被転写樹脂層を形成し、前記被転写樹脂層にモールドを押し付けた状態で前記被転写樹脂層に活性エネルギー線を照射して前記被転写樹脂層を硬化させることによって複数の柱状凸部を形成する工程を備え、前記被転写樹脂層は、反応性フッ素添加剤を含有する樹脂を用いて形成される、撥水性部材の製造方法が提供される。 According to still another aspect of the present invention, a photocurable resin composition is applied on a substrate to form a transferred resin layer, and the transferred resin layer is pressed against the transferred resin layer. A step of forming a plurality of columnar convex portions by irradiating active energy rays to the resin layer to be transferred, and the resin layer to be transferred is formed using a resin containing a reactive fluorine additive A method for producing a water repellent member is provided.
本発明の一実施形態の撥水性部材１を示し、（ａ）は平面図、（ｂ）はＡ－Ａ断面図である。1 shows a water-repellent member 1 according to an embodiment of the present invention, in which (a) is a plan view and (b) is a cross-sectional view along AA. （ａ）～（ｃ）は、本発明の一実施形態の撥水性部材１の製造工程を示す。(A)-(c) shows the manufacturing process of the water-repellent member 1 of one Embodiment of this invention. （ａ）～（ｃ）は、図２から続く、撥水性部材１の製造工程を示す。(A) to (c) show manufacturing steps of the water-repellent member 1 continued from FIG.
　以下、図１～図３を参照しながら本発明の好ましい実施の形態について具体的に説明する。 Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to FIGS.
１．撥水性部材
　本発明の一実施形態の撥水性部材１は、基材６と、基材６の少なくとも一方の面に樹脂層７を備え、樹脂層７は、複数の柱状凸部３を有し、柱状凸部３は、断面積が４００π～２５００πｎｍ２であり、柱状凸部３が形成されるピッチＰが９０～４００ｎｍであり、隣接した２つの柱状凸部３の間の隙間Ｇが５０～３６０ｎｍであり、フッ素原子を含むフッ素原子含有層９が柱状凸部３を覆うように設けられている。柱状凸部３とフッ素原子含有層９の間には無機膜８が設けられていてもよい。柱状凸部３がフッ素原子含有層９で被覆されたものを被覆柱状凸部５と称する。 1. Water-repellent member The water-repellent member 1 of one embodiment of the present invention includes a base 6 and a resin layer 7 on at least one surface of the base 6, and the resin layer 7 has a plurality of columnar protrusions 3. The columnar protrusion 3 has a cross-sectional area of 400π to 2500πnm 2 , a pitch P at which the columnar protrusion 3 is formed is 90 to 400 nm, and a gap G between two adjacent columnar protrusions 3 is 50 to The fluorine atom-containing layer 9 having a thickness of 360 nm and containing fluorine atoms is provided so as to cover the columnar protrusions 3. An inorganic film 8 may be provided between the columnar protrusion 3 and the fluorine atom-containing layer 9. The columnar convex portion 3 covered with the fluorine atom-containing layer 9 is referred to as a coated columnar convex portion 5.
＜撥水性部材１＞
　撥水性部材１の形態は特に限定されないが、可撓性を有する撥水フィルムであることが好ましい。撥水性部材１の水に対する接触角は特に限定されないが、１７０度以上が好ましく、１７５度以上がさらに好ましく、１７８度以上がさらに好ましい。 <Water repellent member 1>
The form of the water repellent member 1 is not particularly limited, but is preferably a flexible water repellent film. Although the contact angle with respect to the water of the water repellent member 1 is not specifically limited, 170 degree | times or more is preferable, 175 degree | times or more is more preferable, 178 degree | times or more is further more preferable.
＜基材６＞
　基材６の材質は、特に限定されないが、樹脂基材、石英基材などの透明基材であることが好ましく、可撓性の観点から樹脂基材であることがさらに好ましい。樹脂基材を構成する樹脂としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリエステル、ポリオレフィン、ポリイミド、ポリサルフォン、ポリエーテルサルフォン、環状ポリオレフィンおよびポリエチレンナフタレートからなる群から選ばれる１種からなるものである。また、基材６は可撓性を有するフィルム状であることが好ましく、その厚さは２５～５００μｍの範囲であることが好ましい。 <Substrate 6>
Although the material of the base material 6 is not specifically limited, It is preferable that they are transparent base materials, such as a resin base material and a quartz base material, and it is more preferable that it is a resin base material from a flexible viewpoint. Examples of the resin constituting the resin base material include one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyester, polyolefin, polyimide, polysulfone, polyethersulfone, cyclic polyolefin, and polyethylene naphthalate. The substrate 6 is preferably in the form of a flexible film, and the thickness is preferably in the range of 25 to 500 μm.
＜樹脂層７、柱状凸部３＞
　樹脂層７を構成する樹脂は特に限定されないが、例えば、（メタ）アクリル樹脂、スチレン樹脂、オレフィン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、エポキシ樹脂、シリコーン樹脂等の樹脂からなり、樹脂の硬さや硬化速度の調整が可能で凹凸の形状を賦型しやすいという理由から（メタ）アクリル樹脂からなることが好ましい。 <Resin layer 7, columnar convex part 3>
The resin constituting the resin layer 7 is not particularly limited. For example, the resin layer 7 is made of a resin such as a (meth) acrylic resin, a styrene resin, an olefin resin, a polycarbonate resin, a polyester resin, an epoxy resin, or a silicone resin. It is preferable to use (meth) acrylic resin for the reason that it is possible to easily adjust the shape of the unevenness.
　柱状凸部３は、その高さ方向に断面積が実質的に一定である凸部である。柱状凸部３の断面形状は円が好ましいが、楕円、長円、多角形（正方形、長方形、正六角形など）などの別の形状であってもよい。柱状凸部３の断面形状が円である場合、その直径は４０～１００ｎｍが好ましく、６０～１００ｎｍがさらに好ましい。この直径は、具体的には例えば、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、９５、１００ｎｍであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。直径が４０ｎｍのときの断面積は４００πｎｍ２であり、直径が１００ｎｍのときの断面積は２５００πｎｍ２である。柱状凸部３は、断面形状が円以外の場合でも、円の場合と同様の断面積を有することが好ましい。従って、柱状凸部３は、断面形状に関わらず、断面積が４００π～２５００πｎｍ２であることが好ましく、９００π～２５００πｎｍ２であることがさらに好ましい。この断面積は、具体的には例えば、４００、５００、６００、７００、８００、９００、１０００、１１００、１２００、１３００、１４００、１５００、１６００、１７００、１８００、１９００、２０００、２１００、２２００、２３００、２４００、２５００πｎｍ２であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The columnar convex part 3 is a convex part whose cross-sectional area is substantially constant in the height direction. The cross-sectional shape of the columnar convex portion 3 is preferably a circle, but may be another shape such as an ellipse, an ellipse, or a polygon (such as a square, a rectangle, or a regular hexagon). When the cross-sectional shape of the columnar convex portion 3 is a circle, the diameter is preferably 40 to 100 nm, and more preferably 60 to 100 nm. This diameter is specifically, for example, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 nm, and between any two of the numerical values exemplified here It may be within the range. The cross-sectional area when the diameter is 40 nm is 400 πnm 2 , and the cross-sectional area when the diameter is 100 nm is 2500 πnm 2 . Even when the cross-sectional shape is other than a circle, the columnar convex portion 3 preferably has the same cross-sectional area as that of a circle. Therefore, the columnar convex portion 3 preferably has a cross-sectional area of 400π to 2500πnm 2 and more preferably 900π to 2500πnm 2 regardless of the cross-sectional shape. Specifically, this cross-sectional area is, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300. 2400 and 2500πnm 2 , and may be within a range between any two of the numerical values exemplified here.
　柱状凸部３が形成されるピッチＰが９０～４００ｎｍであり、隣接した２つの柱状凸部３の間の隙間Ｇが５０～３６０ｎｍである。ピッチＰが小さすぎたり、隙間Ｇが小さすぎる場合には、隣接する柱状凸部３間の間隔が狭くなりすぎて、撥水性が高くなりにくい。また、ピッチＰが大きすぎると柱状凸部３によって構造色が発現されて透明性が損なわれやすくなるからである。ピッチＰは、具体的には例えば、９０、１００、１１０、１２０、１３０、１４０、１５０、１６０、１７０、１８０、１９０、２００、２１０、２２０、２３０、２４０、２５０、２６０、２７０、２８０、２９０、３００、３１０、３２０、３３０、３４０、３５０、３６０、３７０、３８０、３９０、４００ｎｍであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。隙間Ｇは、具体的には例えば、５０、６０、７０、８０、９０、１００、１１０、１２０、１３０、１４０、１５０、１６０、１７０、１８０、１９０、２００、２１０、２２０、２３０、２４０、２５０、２６０、２７０、２８０、２９０、３００、３１０、３２０、３３０、３４０、３５０、３６０ｎｍであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The pitch P at which the columnar protrusions 3 are formed is 90 to 400 nm, and the gap G between two adjacent columnar protrusions 3 is 50 to 360 nm. When the pitch P is too small or the gap G is too small, the interval between the adjacent columnar convex portions 3 becomes too narrow and the water repellency is hardly increased. Further, if the pitch P is too large, a structural color is expressed by the columnar convex portions 3 and transparency is easily impaired. Specifically, the pitch P is, for example, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 nm, and may be within a range between any two of the numerical values exemplified here. Specifically, the gap G is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360 nm, and may be within a range between any two of the numerical values exemplified here.
　柱状凸部３の高さは、特に限定されないが、例えば、５０～４００ｎｍであり、１５０～４００ｎｍが好ましい。柱状凸部３の高さが低すぎると撥水性が高くなりにくく、柱状凸部３の高さが高すぎると柱状凸部３が倒壊されやすくなるからである。柱状凸部３の高さは、具体的には例えば、５０、６０、７０、８０、９０、１００、１１０、１２０、１３０、１４０、１５０、１６０、１７０、１８０、１９０、２００、２１０、２２０、２３０、２４０、２５０、２６０、２７０、２８０、２９０、３００、３１０、３２０、３３０、３４０、３５０、３６０、３７０、３８０、３９０、４００ｎｍであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The height of the columnar protrusion 3 is not particularly limited, but is, for example, 50 to 400 nm, and preferably 150 to 400 nm. This is because if the height of the columnar convex portion 3 is too low, the water repellency is hardly increased, and if the height of the columnar convex portion 3 is too high, the columnar convex portion 3 is likely to collapse. Specifically, the height of the columnar convex portion 3 is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220. , 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 nm, between any two of the numerical values illustrated here It may be within the range.
＜無機膜８・フッ素原子含有層９＞
　フッ素原子含有層９が柱状凸部３を覆うように設けられている。フッ素原子含有層９は、フッ素原子を含んでいればよく、その厚さや構成は限定されない。フッ素原子含有層９を設けることによって撥水性が高められる。フッ素原子含有層９は、フッ素含有基を含むことが好ましい。フッ素含有基は、一例では、パーフルオロアルキル基であり、より具体的には、パーフルオロアルキルシラン基である。パーフルオロアルキル基の炭素数は、例えば１～１０であり、具体的には例えば、１、２、３、４、５、６、７、８、９、１０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。フッ素含有基は、好ましくは、柱状凸部３又は無機膜８に化学結合されている。一般に、無機膜８は樹脂層７との密着性が高く、フッ素含有基は、無機膜８に対して強固な化学結合を形成しやすいので、柱状凸部３とフッ素原子含有層９の間に無機膜８を設けることによってフッ素原子含有層９が柱状凸部３上に強固に保持される。無機膜８としては、無機酸化膜、無機窒化膜、無機酸窒化膜などが挙げられる。無機膜８を構成する無機元素しては、ＳｉやＡｌが挙げられる。無機膜８は、例えば、酸化シリコン膜や酸化アルミニウム膜である。無機膜８の厚さは、特に限定されないが、例えば、１～２０ｎｍである。 <Inorganic film 8 / fluorine atom-containing layer 9>
A fluorine atom-containing layer 9 is provided so as to cover the columnar protrusion 3. The fluorine atom-containing layer 9 only needs to contain fluorine atoms, and its thickness and configuration are not limited. By providing the fluorine atom-containing layer 9, the water repellency is enhanced. The fluorine atom-containing layer 9 preferably contains a fluorine-containing group. In one example, the fluorine-containing group is a perfluoroalkyl group, and more specifically, a perfluoroalkylsilane group. The carbon number of the perfluoroalkyl group is, for example, 1 to 10, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the numerical values exemplified here are It may be within a range between any two. The fluorine-containing group is preferably chemically bonded to the columnar protrusion 3 or the inorganic film 8. In general, the inorganic film 8 has high adhesion to the resin layer 7, and the fluorine-containing group tends to form a strong chemical bond to the inorganic film 8, so that the columnar convex portion 3 and the fluorine atom-containing layer 9 are interposed. By providing the inorganic film 8, the fluorine atom-containing layer 9 is firmly held on the columnar protrusion 3. Examples of the inorganic film 8 include an inorganic oxide film, an inorganic nitride film, and an inorganic oxynitride film. Examples of inorganic elements constituting the inorganic film 8 include Si and Al. The inorganic film 8 is, for example, a silicon oxide film or an aluminum oxide film. The thickness of the inorganic film 8 is not particularly limited, but is, for example, 1 to 20 nm.
　フッ素原子含有層９は、一例では、柱状凸部３上に無機膜８を形成し、無機膜８とフッ素含有シランカップリング剤を反応させることによって形成することができる。フッ素含有シランカップリング剤は、例えば、パーフルオロアルキルトリアルコキシ（メトキシ、エトキシなど）シランである。無機膜８を形成せずに柱状凸部３にフッ素含有シランカップリング剤を作用させても強固な化学結合が形成されにくいので、予め柱状凸部３上に無機膜８を形成することが好ましい。フッ素含有シランカップリング剤の例としては、オプツールＤＳＸ（ダイキン工業社製）が挙げられる。 In one example, the fluorine atom-containing layer 9 can be formed by forming the inorganic film 8 on the columnar convex portion 3 and reacting the inorganic film 8 with the fluorine-containing silane coupling agent. The fluorine-containing silane coupling agent is, for example, perfluoroalkyltrialkoxy (methoxy, ethoxy, etc.) silane. Even if a fluorine-containing silane coupling agent is allowed to act on the columnar convex portion 3 without forming the inorganic film 8, it is difficult to form a strong chemical bond. Therefore, it is preferable to form the inorganic film 8 on the columnar convex portion 3 in advance. . Examples of the fluorine-containing silane coupling agent include OPTOOL DSX (manufactured by Daikin Industries).
２．撥水性部材の製造方法
　次に、図２～図３を用いて、撥水性部材の製造方法について説明する。 2. Method for Producing Water-Repellent Member Next, a method for producing a water-repellent member will be described with reference to FIGS.
　本発明の一実施形態の撥水性部材の製造方法は、被転写樹脂層形成工程、柱状凸部形成工程と、無機膜形成工程と、フッ素原子含有層形成工程を備える。
　以下、各工程についてさらに詳細に説明する。 The manufacturing method of the water-repellent member of one embodiment of the present invention includes a transferred resin layer forming step, a columnar convex portion forming step, an inorganic film forming step, and a fluorine atom-containing layer forming step.
Hereinafter, each step will be described in more detail.
＜被転写樹脂層形成工程＞
　まず、図２（ａ）に示すように、基材６上に光硬化性樹脂組成物を塗布して被転写樹脂層１１を形成する。基材６の詳細は上述した通りである。光硬化性樹脂組成物は、モノマーと、光開始剤を含有し、活性エネルギー線の照射によって硬化する性質を有する。「活性エネルギー線」は、ＵＶ光、可視光、電子線などの、光硬化性樹脂組成物を硬化可能なエネルギー線の総称である。 <Transferable resin layer forming step>
First, as shown in FIG. 2A, a photocurable resin composition is applied on a substrate 6 to form a transferred resin layer 11. The details of the substrate 6 are as described above. The photocurable resin composition contains a monomer and a photoinitiator and has a property of being cured by irradiation with active energy rays. “Active energy rays” is a general term for energy rays that can cure a photocurable resin composition, such as UV light, visible light, and electron beams.
　モノマーとしては、（メタ）アクリル樹脂、スチレン樹脂、オレフィン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、エポキシ樹脂、シリコーン樹脂等を形成するための光重合性のモノマーが挙げられ、光重合性の（メタ）アクリル系モノマーが好ましい。なお、本明細書において、（メタ）アクリルとは、メタクリルおよび／またはアクリルを意味し、（メタ）アクリレートはメタクリレートおよび／またはアクリレートを意味する。 Monomers include photopolymerizable monomers for forming (meth) acrylic resins, styrene resins, olefin resins, polycarbonate resins, polyester resins, epoxy resins, silicone resins, etc., and photopolymerizable (meth) acrylic. System monomers are preferred. In the present specification, (meth) acryl means methacryl and / or acryl, and (meth) acrylate means methacrylate and / or acrylate.
　光開始剤は、モノマーの重合を促進するために添加される成分であり、前記モノマー１００質量部に対して０．１質量部以上含有されることが好ましい。光開始剤の含有量の上限は、特に規定されないが、例えば前記モノマー１００質量部に対して２０質量部である。 The photoinitiator is a component added to promote the polymerization of the monomer, and is preferably contained in an amount of 0.1 part by mass or more with respect to 100 parts by mass of the monomer. Although the upper limit of content of a photoinitiator is not prescribed | regulated in particular, For example, it is 20 mass parts with respect to 100 mass parts of said monomers.
　光硬化性樹脂組成物は、溶剤、重合禁止剤、連鎖移動剤、酸化防止剤、光増感剤、充填剤、レベリング剤等の成分を光硬化性樹脂組成物の性質に影響を与えない範囲で含んでいてもよい。 The photocurable resin composition is a range in which components such as a solvent, a polymerization inhibitor, a chain transfer agent, an antioxidant, a photosensitizer, a filler, and a leveling agent do not affect the properties of the photocurable resin composition. May be included.
　光硬化性樹脂組成物は、上記成分を公知の方法で混合することにより製造することができる。光硬化性樹脂組成物は、スピンコート、スプレーコート、バーコート、ディップコート、ダイコートおよびスリットコート等の方法で基材６上に塗布して被転写樹脂層１１を形成することが可能である。 The photocurable resin composition can be produced by mixing the above components by a known method. The photocurable resin composition can be applied on the substrate 6 by a method such as spin coating, spray coating, bar coating, dip coating, die coating, and slit coating to form the transferred resin layer 11.
＜柱状凸部形成工程＞
　次に、図２（ａ）～図２（ｂ）に示すように、被転写樹脂層１１に対して、ベース柱状凸部４の反転パターン１５を有するモールド１３を押し付けた状態で被転写樹脂層１１に活性エネルギー線１７を照射して被転写樹脂層１１を硬化させることによって、ベース柱状凸部４を有する樹脂層７を形成する。つまり、ベース柱状凸部４は、モールド１３を用いてナノインプリント法によって形成される。ベース柱状凸部４は、所望の柱状凸部３よりも大きいサイズになるように形成する。 <Columnar convex formation process>
Next, as shown in FIG. 2A to FIG. 2B, the transferred resin layer in a state where the mold 13 having the reverse pattern 15 of the base columnar convex portion 4 is pressed against the transferred resin layer 11. The resin layer 7 having the base columnar convex portions 4 is formed by curing the transferred resin layer 11 by irradiating the active energy rays 17 to the substrate 11. That is, the base columnar convex portion 4 is formed by the nanoimprint method using the mold 13. The base columnar protrusion 4 is formed to have a size larger than the desired columnar protrusion 3.
　モールド１３の種類は特に限定されないが、例えば、樹脂製モールド、ニッケル製モールドなどが利用可能である。モールド１３を被転写樹脂層１１に押し付ける圧力は、反転パターン１５の形状を被転写樹脂層１１に転写可能な圧力であればよい。被転写樹脂層１１へ照射する活性エネルギー線１７は、被転写樹脂層１１が十分に硬化する程度の積算光量で照射すればよく、積算光量は、例えば１００～１００００ｍＪ／ｃｍ２である。活性エネルギー線１７の照射によって、被転写樹脂層１１が硬化される。本実施形態では、基材６側から活性エネルギー線１７の照射を行っているが、モールド側から活性エネルギー線１７の照射を行ってもよい。 The type of the mold 13 is not particularly limited. For example, a resin mold, a nickel mold, or the like can be used. The pressure for pressing the mold 13 against the transferred resin layer 11 may be any pressure that can transfer the shape of the reversal pattern 15 to the transferred resin layer 11. The active energy ray 17 applied to the transferred resin layer 11 may be irradiated with an integrated light amount sufficient to sufficiently cure the transferred resin layer 11, and the integrated light amount is, for example, 100 to 10,000 mJ / cm 2 . The transferred resin layer 11 is cured by irradiation with the active energy ray 17. In the present embodiment, the active energy rays 17 are irradiated from the substrate 6 side, but the active energy rays 17 may be irradiated from the mold side.
　次に、モールド１３を取り外すことによって、図２（ｃ）に示すように、基材６上に複数のベース柱状凸部４を有する樹脂層７が形成された構造が得られる。なお、モールド１３を取り外すときに、未硬化の光硬化性樹脂組成物を溶剤で洗い流してもよい。 Next, by removing the mold 13, as shown in FIG. 2C, a structure in which the resin layer 7 having the plurality of base columnar protrusions 4 is formed on the base material 6 is obtained. When removing the mold 13, the uncured photocurable resin composition may be washed away with a solvent.
　次に、図２（ｃ）～図３（ａ）に示すように、酸素プラズマアッシング処理を行ってベース柱状凸部４を縮小させて柱状凸部３を形成する。酸素プラズマアッシング処理の条件は、所望の形状の柱状凸部４を得るべく適宜設定することができる。このように、本実施形態では、ナノインプリント法によってベース柱状凸部４を形成した後に酸素プラズマアッシング処理でベース柱状凸部４のサイズを縮小させることによって所望形状の柱状凸部３を得ているので、１つのモールド１３を用いて、柱状凸部３の形状が互いに異なる種々の撥水性部材を得ることができる。 Next, as shown in FIGS. 2C to 3A, an oxygen plasma ashing process is performed to reduce the base columnar protrusions 4 to form the columnar protrusions 3. The conditions for the oxygen plasma ashing treatment can be set as appropriate to obtain the columnar convex portions 4 having a desired shape. Thus, in this embodiment, since the columnar convex part 4 of desired shape is obtained by reducing the size of the base columnar convex part 4 by the oxygen plasma ashing process after forming the base columnar convex part 4 by the nanoimprint method. Using one mold 13, various water repellent members having different columnar convex portions 3 can be obtained.
　なお、ナノインプリント法によってベース柱状凸部４を形成する代わりに、柱状凸部３の反転パターン１５を有するモールド１３を用いて、ナノインプリント法によって、柱状凸部３を直接形成してもよい。この場合、酸素プラズマアッシング処理工程を省略することができる。 In addition, instead of forming the base columnar convex portion 4 by the nanoimprint method, the columnar convex portion 3 may be directly formed by the nanoimprint method using the mold 13 having the reverse pattern 15 of the columnar convex portion 3. In this case, the oxygen plasma ashing process can be omitted.
　ところで、被転写樹脂層１１は、反応性フッ素添加剤を含有する樹脂を用いて形成してもよい。反応性フッ素添加剤とは、光（例：ＵＶ）反応性基とフッ素含有基とを備える化合物である。この場合、被転写樹脂層１１に活性エネルギー線１７を照射すると、フッ素含有基が樹脂層７の表面に露出して柱状凸部３を覆うフッ素原子含有層９が形成される。従って、この場合、フッ素原子含有層９を別途形成することなく、優れた撥水性が発揮される。反応性フッ素添加剤の例としては、メガファックＲＳシリーズ（ＤＩＣ社製）が挙げられる。 Incidentally, the transferred resin layer 11 may be formed using a resin containing a reactive fluorine additive. A reactive fluorine additive is a compound comprising a light (eg, UV) reactive group and a fluorine-containing group. In this case, when the active energy ray 17 is irradiated to the transferred resin layer 11, the fluorine-containing group 9 is formed so that the fluorine-containing group is exposed on the surface of the resin layer 7 and covers the columnar protrusions 3. Therefore, in this case, excellent water repellency is exhibited without separately forming the fluorine atom-containing layer 9. As an example of the reactive fluorine additive, Megafac RS series (manufactured by DIC) may be mentioned.
＜無機膜形成工程＞
　次に、図３（ｂ）に示すように、柱状凸部３を覆うように無機膜８を形成する。無機膜８は、蒸着やスパッタリングなどの方法で形成可能である。図３（ｂ）では、無機膜８は、柱状凸部３の上面及び側面の両方を覆っているが、無機膜８は、柱状凸部３の少なくとも一部を覆うように形成すればよく、例えば、柱状凸部３の上面のみを覆うように形成してもよい。また、図３（ｂ）では、無機膜８は、樹脂層７の全面を覆うように形成しているが、柱状凸部３のみを覆うように形成してもよい。 <Inorganic film forming process>
Next, as shown in FIG. 3B, an inorganic film 8 is formed so as to cover the columnar protrusions 3. The inorganic film 8 can be formed by a method such as vapor deposition or sputtering. In FIG. 3B, the inorganic film 8 covers both the upper surface and the side surface of the columnar convex portion 3, but the inorganic film 8 may be formed so as to cover at least a part of the columnar convex portion 3, For example, you may form so that only the upper surface of the columnar convex part 3 may be covered. In FIG. 3B, the inorganic film 8 is formed so as to cover the entire surface of the resin layer 7, but may be formed so as to cover only the columnar convex portions 3.
＜フッ素原子含有層形成工程＞
　次に、図３（ｃ）に示すように、無機膜８とフッ素含有シランカップリング剤を反応させることによって無機膜８を覆うようにフッ素原子含有層９を形成する。図３（ｃ）では、フッ素原子含有層９は、柱状凸部３の上面及び側面の両方を覆っているが、フッ素原子含有層９は、柱状凸部３の少なくとも一部を覆うように形成すればよく、例えば、柱状凸部３の上面のみを覆うように形成してもよい。また、図３（ｃ）では、フッ素原子含有層９は、樹脂層７の全面を覆うように形成しているが、柱状凸部３のみを覆うように形成してもよい。また、図３（ｃ）では、何れの領域においても、フッ素原子含有層９と樹脂層７の間に無機膜８が存在しているが、一部の領域においてはフッ素原子含有層９と樹脂層７が直接接触するようにしてもよい。 <Fluorine atom-containing layer forming step>
Next, as shown in FIG. 3C, a fluorine atom-containing layer 9 is formed so as to cover the inorganic film 8 by reacting the inorganic film 8 with a fluorine-containing silane coupling agent. In FIG. 3C, the fluorine atom-containing layer 9 covers both the upper surface and the side surface of the columnar convex portion 3, but the fluorine atom-containing layer 9 is formed so as to cover at least a part of the columnar convex portion 3. For example, you may form so that only the upper surface of the columnar convex part 3 may be covered. In FIG. 3C, the fluorine atom-containing layer 9 is formed so as to cover the entire surface of the resin layer 7, but may be formed so as to cover only the columnar protrusions 3. In FIG. 3C, the inorganic film 8 is present between the fluorine atom-containing layer 9 and the resin layer 7 in any region, but in some regions, the fluorine atom-containing layer 9 and the resin are present. The layer 7 may be in direct contact.
＜産業上の利用可能性＞
本発明の撥水性部材は、輸送機器、建造物および通信機器に用いられる窓、レンズ、ディスプレイ、センサーなどのほか、結露防止が必要な物品（空調設備、熱交換器、コンデンサなど）、換気扇、アクチュエータ、燃料電池用電極、ノズル、フィルタ、防水施工用シート、化粧板、道路上への設置物（交通標識、信号機、防音壁、交通案内板、ブリンカーライト）などに好適に利用できる。 <Industrial applicability>
The water-repellent member of the present invention is a window, lens, display, sensor, etc. used for transportation equipment, buildings and communication equipment, as well as articles that require dew condensation prevention (air conditioning equipment, heat exchangers, condensers, etc.), ventilation fans, It can be suitably used for actuators, fuel cell electrodes, nozzles, filters, waterproof construction sheets, decorative boards, road installations (traffic signs, traffic lights, soundproof walls, traffic guide boards, blinker lights), and the like.
　以下、本発明の実施例及び比較例を示す。サンプル３～４及び９が本発明の実施例であり、残りのサンプルが比較例である。 Hereinafter, examples and comparative examples of the present invention will be described. Samples 3 to 4 and 9 are examples of the present invention, and the remaining samples are comparative examples.
＜ＵＶ硬化樹脂の調製＞
　まず、多官能モノマー及び光開始剤を以下に示す割合で配合してＵＶ硬化樹脂を調製した。
多官能アクリレートモノマー
　ビスコート＃３６０（大阪有機化学工業社製）５０質量部
　ビスコート＃７００ＨＶ　（大阪有機化学工業社製）　２０質量部
　ビスコート＃３１０ＨＰ　（大阪有機化学工業社製）　３０質量部
光開始剤
　イルガキュア１８４（ＢＡＳＦジャパン社製）　５質量部 <Preparation of UV curable resin>
First, a polyfunctional monomer and a photoinitiator were blended in the proportions shown below to prepare a UV curable resin.
Multifunctional acrylate monomer Biscoat # 360 (manufactured by Osaka Organic Chemical Industry) 50 parts by mass Biscoat # 700HV (manufactured by Osaka Organic Chemical Industry) 20 parts by mass Biscoat # 310HP (manufactured by Osaka Organic Chemical Industry) 30 parts by mass Photoinitiator Irgacure 184 (manufactured by BASF Japan) 5 parts by mass
＜サンプルの作製＞
［サンプル１］
　ＰＥＴ基材に対して、上記調製のＵＶ硬化樹脂を５μｍ厚になるようにバーコーターで塗工をし、ナノホール形状（周期２４０ｎｍ，直径１４０ｎｍ，深さ２５０ｎｍ）モールドに対して、塗工した樹脂面をモールドに押し当てるように上からローラーでラミネートを行った。その後、ＰＥＴ基材側から積算光量５００ｍＪ／ｃｍ２でＵＶ照射を行い、ＵＶ硬化樹脂を硬化させた。モールドと樹脂硬化させたＰＥＴ基材を剥離し、上記モールドの反転形状であるナノピラー転写品を作製した。 <Preparation of sample>
[Sample 1]
The UV curable resin prepared above was applied to a PET substrate with a bar coater to a thickness of 5 μm, and applied to a nanohole mold (period 240 nm, diameter 140 nm, depth 250 nm). Lamination was performed with a roller from above so that the surface was pressed against the mold. Thereafter, UV irradiation was performed from the PET substrate side with an integrated light amount of 500 mJ / cm 2 to cure the UV curable resin. The mold and the resin-cured PET base material were peeled off to produce a nanopillar transfer product having the inverted shape of the mold.
　その後、バッチ型真空製膜装置で、賦型した表面に対して、ビーム電圧５００［Ｖ］，ビーム電流４００［ｍＡ］、製膜圧力１［Ｐａ］以下の条件において、ＳｉＯ２の蒸着処理を行い、ＳｉＯ２の薄膜を皮膜させた。そして、フッ素含有シランカップリング剤（ダイキン工業社製、オプツールＤＳＸ）をその表面に塗布し、温度５０℃湿度８０％の条件下で反応させて、表面をフッ素化処理することによってフッ素原子含有層を形成した撥水性フィルム（サンプル１）を作製した。 After that, with a batch type vacuum film forming apparatus, SiO 2 is deposited on the shaped surface under conditions of a beam voltage of 500 [V], a beam current of 400 [mA], and a film forming pressure of 1 [Pa]. Then, a thin film of SiO 2 was coated. Then, a fluorine-containing silane coupling agent (Daikin Kogyo Co., Ltd., OPTOOL DSX) is applied to the surface, reacted under conditions of a temperature of 50 ° C. and a humidity of 80%, and the surface is fluorinated so that the fluorine atom-containing layer A water-repellent film (Sample 1) was formed.
［サンプル２～４］
　サンプル１と同様の方法で作製したナノピラー転写品に対して、プラズマクリーナー（Ｓａｍｃｏ製、型式：ＰＣ－３００）を用いて、５０［Ｐａ］以下の真空下において、高周波（１３．５６ＭＨｚ）を２００ｗの条件で酸素プラズマアッシング処理を施し、転写品のＵＶ硬化樹脂を削り、形状の直径を細くした。その際、処理時間によって、直径の異なるものを作製した。その後、サンプル１と同様の方法で表面のフッ素化処理を行って、撥水性フィルム（サンプル２～４）を作製した。 [Samples 2 to 4]
Using a plasma cleaner (Samco, model: PC-300), a nano-pillar transfer product produced by the same method as Sample 1 is applied with a high frequency (13.56 MHz) of 200 w under a vacuum of 50 [Pa] or less. Oxygen plasma ashing was performed under the conditions described above, and the UV cured resin of the transferred product was shaved to reduce the shape diameter. At that time, different diameters were produced depending on the treatment time. Thereafter, the surface was fluorinated by the same method as in Sample 1 to produce water-repellent films (Samples 2 to 4).
［サンプル５～８］
　ナノピラー形状（周期２４０ｎｍ，直径１６０ｎｍ，高さ２５０ｎｍ）モールドを用いた以外は、サンプル１～４と同様の方法で撥水性フィルム（サンプル５～８）を作製した。 [Samples 5-8]
Water-repellent films (samples 5 to 8) were prepared in the same manner as samples 1 to 4, except that a nanopillar mold (period 240 nm, diameter 160 nm, height 250 nm) was used.
［サンプル９］
　上記のＵＶ硬化樹脂に反応性フッ素添加剤（ＤＩＣ社製、メガファックＲＳ－７５）を１０部添加させた混合物をＰＥＴ基材に５μｍ厚になるように、バーコーターで塗工し、それをナノホール形状（周期２４０ｎｍ，直径６０ｎｍ，深さ２５０ｎｍ）モールドに対して、樹脂面を押し当てるようにラミネート行った。その後、ＰＥＴ基材側から積算光量１０００ｍＪ／ｃｍ２でＵＶ照射を行って硬化をさせ、ＰＥＴ基材をモールドから離型し、上記の反転形状の転写品を作製した。さらに、作製した転写品に対して、フッ素含有シランカップリング剤（ダイキン工業社製、オプツールＤＳＸ）を塗布し、表面をフッ素処理することによってフッ素原子含有層を形成した撥水性フィルム（サンプル９）を作製した。 [Sample 9]
A mixture obtained by adding 10 parts of the reactive fluorine additive (manufactured by DIC, Megaface RS-75) to the above UV curable resin was applied to a PET substrate with a bar coater so as to have a thickness of 5 μm. Lamination was performed so that the resin surface was pressed against a nanohole-shaped (period 240 nm, diameter 60 nm, depth 250 nm) mold. Thereafter, UV irradiation was performed from the PET base material side with an integrated light amount of 1000 mJ / cm 2 to cure, and the PET base material was released from the mold to produce the above-mentioned inverted transfer product. Further, a water-repellent film (Sample 9) in which a fluorine-containing silane coupling agent (manufactured by Daikin Industries, Optool DSX) was applied to the produced transfer product and the surface was subjected to fluorine treatment to form a fluorine atom-containing layer (Sample 9) Was made.
［サンプル１０～１１］
　モスアイ形状の反転パターンを有するモールドを用いた以外は、サンプル１と同様の方法により、撥水性フィルム（サンプル１０～１１）を作製した。 [Samples 10 to 11]
Water-repellent films (Samples 10 to 11) were produced in the same manner as Sample 1, except that a mold having a moth-eye-shaped reversal pattern was used.
［サンプル１２］
　サンプル１１の撥水性フィルムに対して、サンプル２～４と同様の方法で酸素プラズマアッシング処理を施してサンプル１２とした。 [Sample 12]
Sample 12 was subjected to oxygen plasma ashing treatment on the water repellent film of Sample 11 in the same manner as Samples 2-4.
＜直径、周期、高さ測定＞
　サンプルの一部を切除して、走査型電子顕微鏡（日本電子社製、型式：ＪＳＭ－７８００Ｆ）を用いて形状を観察し、同顕微鏡に付属するソフトウェア（ＰＣ-ＳＵＭ）を用いて測定した。なお、直径は高さの中央部分に合わせて測定した。 <Diameter, period, height measurement>
A part of the sample was excised, the shape was observed using a scanning electron microscope (manufactured by JEOL Ltd., model: JSM-7800F), and measurement was performed using software (PC-SUM) attached to the microscope. In addition, the diameter was measured according to the center part of height.
＜水接触角測定＞
　得られた撥水性フィルムについて、接触角測定装置（ｄａｔａｐｈｙｓｉｃｓ社製）を用いて、室温（２５℃）下において、当該フィルムの表面にイオン交換水０．５μｌ滴下し、フィルムと水の接する角度（水接触角）を測定した。 <Water contact angle measurement>
With respect to the obtained water-repellent film, 0.5 μl of ion-exchanged water was dropped on the surface of the film at room temperature (25 ° C.) using a contact angle measuring device (manufactured by dataphysics). Water contact angle) was measured.
　各サンプルの形状の詳細と水接触角測定結果を表１に示す。 Table 1 shows the details of the shape of each sample and the water contact angle measurement results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本発明の実施例であるサンプル３，４，９の撥水性フィルムは、撥水性が非常に優れていたが、残りのサンプルの撥水性フィルムは、実施例のサンプルよりも撥水性が劣っていた。 As shown in Table 1, the water-repellent films of Samples 3, 4 and 9 as examples of the present invention were very excellent in water repellency, but the water-repellent films of the remaining samples were more than the samples of Examples. The water repellency was poor.
１：撥水性部材、３：柱状凸部、４：ベース柱状凸部、５：被覆柱状凸部、６：基材、７：樹脂層、８：無機膜、９：フッ素原子含有層、１１：被転写樹脂層、１３：モールド、１５：反転パターン、１７：活性エネルギー線 1: water-repellent member, 3: columnar convex portion, 4: base columnar convex portion, 5: coated columnar convex portion, 6: base material, 7: resin layer, 8: inorganic film, 9: fluorine atom-containing layer, 11: Transferred resin layer, 13: mold, 15: reverse pattern, 17: active energy ray

Claims (14)

  1. 基材と、前記基材の少なくとも一方の面に樹脂層を備え、
    前記樹脂層は、複数の柱状凸部を有し、
    前記柱状凸部は、断面積が４００π～２５００πｎｍ２であり、
    前記柱状凸部が形成されるピッチが９０～４００ｎｍであり、
    隣接した２つの柱状凸部の間の隙間が５０～３６０ｎｍであり、
    フッ素原子を含むフッ素原子含有層が前記柱状凸部を覆うように設けられている、撥水性部材。     A substrate and a resin layer on at least one surface of the substrate;
    The resin layer has a plurality of columnar protrusions,
    The columnar convex portion has a cross-sectional area of 400π to 2500πnm 2 ,
    The pitch at which the columnar protrusions are formed is 90 to 400 nm,
    The gap between two adjacent columnar protrusions is 50 to 360 nm,
    A water-repellent member provided with a fluorine atom-containing layer containing fluorine atoms so as to cover the columnar protrusions.
  2. 前記フッ素原子含有層は、フッ素含有基を含む、請求項１に記載の撥水性部材。 The water repellent member according to claim 1, wherein the fluorine atom-containing layer contains a fluorine-containing group.
  3. 前記柱状凸部と前記フッ素原子含有層の間に無機膜を備える、請求項２に記載の撥水性部材。 The water repellent member according to claim 2, further comprising an inorganic film between the columnar convex portion and the fluorine atom-containing layer.
  4. 前記フッ素含有基は、パーフルオロアルキル基である、請求項２又は請求項３に記載の撥水性部材。 The water repellent member according to claim 2 or 3, wherein the fluorine-containing group is a perfluoroalkyl group.
  5. 前記柱状凸部は、断面積が９００π～２５００πｎｍ２である、請求項１～請求項４の何れか１つに記載の撥水性部材。 The columnar convex part, the cross-sectional area is 900π ~ 2500πnm 2, water-repellent member according to any one of claims 1 to 4.
  6. 前記柱状凸部は、円柱状である、請求項１～請求項５の何れか１つに記載の撥水性部材。 The water repellent member according to any one of claims 1 to 5, wherein the columnar convex portion has a cylindrical shape.
  7. 前記柱状凸部は、高さが５０～４００ｎｍである、請求項１～請求項６の何れか１つに記載の撥水性部材。 The water repellent member according to any one of claims 1 to 6, wherein the columnar convex portion has a height of 50 to 400 nm.
  8. 前記柱状凸部は、高さが１５０～４００ｎｍである、請求項１～請求項７の何れか１つに記載の撥水性部材。 The water-repellent member according to any one of claims 1 to 7, wherein the columnar protrusion has a height of 150 to 400 nm.
  9. 前記樹脂層は、（メタ）アクリル樹脂からなる、請求項１～請求項８の何れか１つに記載の撥水性部材。 The water repellent member according to any one of claims 1 to 8, wherein the resin layer is made of (meth) acrylic resin.
  10. 水に対する接触角が１７０度以上である、請求項１～請求項９の何れか１つに記載の撥水性部材。 The water repellent member according to any one of claims 1 to 9, wherein a contact angle with water is 170 degrees or more.
  11. 基材上に光硬化性樹脂組成物を塗布して形成した被転写樹脂層に複数の柱状凸部を形成し、
    前記柱状凸部を覆うように無機膜を形成し、
    前記無機膜とフッ素含有シランカップリング剤を反応させることによって前記無機膜を覆うようにフッ素原子含有層を形成する工程を備える、撥水性部材の製造方法。     A plurality of columnar protrusions are formed on a transferred resin layer formed by applying a photocurable resin composition on a substrate,
    Forming an inorganic film so as to cover the columnar protrusions;
    A method for producing a water-repellent member, comprising a step of forming a fluorine atom-containing layer so as to cover the inorganic film by reacting the inorganic film with a fluorine-containing silane coupling agent.
  12. 前記柱状凸部は、モールドを用いてナノインプリント法によって形成される、請求項１１に記載の撥水性部材の製造方法。 The said columnar convex part is a manufacturing method of the water-repellent member of Claim 11 formed by the nanoimprint method using a mold.
  13. 前記柱状凸部は、モールドを用いてナノインプリント法によってベース柱状凸部を形成した後に酸素プラズマアッシング処理を行って前記ベース柱状凸部を縮小させることによって形成される、請求項１１に記載の撥水性部材の製造方法。 The water repellent according to claim 11, wherein the columnar protrusion is formed by forming a base columnar protrusion by a nanoimprint method using a mold and then performing an oxygen plasma ashing process to reduce the base columnar protrusion. Manufacturing method of member.
  14. 基材上に光硬化性樹脂組成物を塗布して被転写樹脂層を形成し、
    前記被転写樹脂層にモールドを押し付けた状態で前記被転写樹脂層に活性エネルギー線を照射して前記被転写樹脂層を硬化させることによって複数の柱状凸部を形成する工程を備え、
    前記被転写樹脂層は、反応性フッ素添加剤を含有する樹脂を用いて形成される、撥水性部材の製造方法。     A photocurable resin composition is applied onto a substrate to form a transferred resin layer,
    Including a step of forming a plurality of columnar protrusions by irradiating the transferred resin layer with an active energy ray while the mold is pressed against the transferred resin layer to cure the transferred resin layer.
    The method for producing a water-repellent member, wherein the transferred resin layer is formed using a resin containing a reactive fluorine additive.
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