WO2020195987A1 - フィルム - Google Patents
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- WO2020195987A1 WO2020195987A1 PCT/JP2020/011301 JP2020011301W WO2020195987A1 WO 2020195987 A1 WO2020195987 A1 WO 2020195987A1 JP 2020011301 W JP2020011301 W JP 2020011301W WO 2020195987 A1 WO2020195987 A1 WO 2020195987A1
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- Prior art keywords
- film
- oil
- coating film
- containing layer
- resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04H—BUILDINGS OR LIKE STRUCTURES FOR PARTICULAR PURPOSES; SWIMMING OR SPLASH BATHS OR POOLS; MASTS; FENCING; TENTS OR CANOPIES, IN GENERAL
- E04H9/00—Buildings, groups of buildings or shelters adapted to withstand or provide protection against abnormal external influences, e.g. war-like action, earthquake or extreme climate
- E04H9/16—Buildings, groups of buildings or shelters adapted to withstand or provide protection against abnormal external influences, e.g. war-like action, earthquake or extreme climate against adverse conditions, e.g. extreme climate, pests
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Definitions
- the present invention relates to a film, and more particularly to a film used as a surface covering material for preventing snow or ice from adhering to the surface of an object such as an aircraft, a railroad, an automobile, a wind generator, a house, a traffic light, or a signboard.
- the adhesion of ice to the surface of an object (icing) and the adhesion of snowflakes due to snowfall (snow accretion) are causes of damage and obstacles in various fields.
- icing on aircraft wings, snow accretion / freezing on the lower part of locomotives, snow accretion on automobile headlights, icing on wind power generator blades, snow accretion / freezing on signal lights, etc. can be obstacles to operation, operation and safety.
- snow accretion / freezing on the roofs of houses and signboards may cause damage to these structures and damage to people due to falling snow.
- Patent Document 1 a plurality of grooves extending in one direction are arranged on at least a part of a solid surface to form irregularities at intervals of 2 ⁇ m or more and 4 mm or less, and the convex portions of the irregularities are formed with a water contact angle of 30.
- a snow-sliding solid having a hydrophilicity of ° or less and a recess having a water repellency of 90 ° or more at a water contact angle has been proposed.
- Patent Document 2 a top portion formed in a line shape along a predetermined direction and a recess portion formed in a line shape along the predetermined direction at a position lower than the top portion and adjacent to the top portion are described.
- a snow accretion / snow accretion film or sheet having a curved surface that curves concavely along the vertical direction has been proposed.
- a film or sheet having a snow-sliding function as described above is expected to have the effect of removing snow and ice on the surface of the structure, but as the amount of snowfall per hour increases, the amount of accumulation on the structure also increases, so the time is shorter. It was desired to make the snow slide naturally, and further improvement of the snow-sliding property was required.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a film capable of improving snow accretion and / or preventing snow accretion and / or icing on a structure.
- the present invention includes an oil-containing layer containing an oil component in the resin as the outermost layer, the oil component bleeds from the surface of the oil-containing layer at a predetermined temperature or lower, and the surface of the oil-containing layer is uneven.
- a film having a shape and having a calculated average height (Sa) of 4 ⁇ m or more in a region of 3.2 cm ⁇ 3.2 cm on the surface of the oil-containing layer.
- the calculated average height (Sa) is preferably 10 ⁇ m or more.
- the maximum pitch-to-pitch distance of the uneven shape is preferably 2000 ⁇ m or more.
- the film is preferably a film for preventing snow and ice from accumulating on the surface of an object over time.
- the present invention also provides a method for producing a film, which comprises the following steps (a) and (b) or (c).
- a step of forming a coating film using a resin composition containing a polymer component and an oil component to form an uneven shape on the surface of the coating film (b) The coating film on which the uneven shape is formed.
- Step of Curing (c) A coating film is formed using a resin composition containing a polymer component and an oil component, and after the coating film is cured, a member having irregularities on the surface is formed on one surface of the cured coating film. The process of forming an uneven shape on the surface of the coating film
- the film of the present invention is composed of an oil-containing layer containing an oil component that bleeds on the surface of the film at a predetermined temperature or lower, and further, since the surface is provided with an uneven shape, the snow-sliding property is improved and the structure is formed.
- the attached snow mass and ice can be naturally dropped in a shorter time.
- the term "film” means a film and a sheet as defined in JIS K 6900: 1994.
- a film is a thin, flat product that is extremely small in thickness and width relative to its length and width, and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of rolls.
- a sheet is a thin product, and generally a flat product whose thickness is small for its length and width. The boundary between film and sheet is uncertain, and the concept of sheet is also included in the present specification. Further, in the present specification, “mass” is synonymous with "weight”.
- the film of the present invention contains an oil-containing layer containing an oil component in the resin as the outermost layer, and the surface of the oil-containing layer has an uneven shape.
- the oil component bleeds from the surface of the oil-containing layer at a predetermined temperature or lower and covers the film surface.
- snow blocks and ice adhering to the surface of the film form a portion that does not come into direct contact with the film, so that the frictional force is reduced and the film is easily dropped due to its own weight.
- the slipperiness of the film surface is further improved by the bleeding oil component. Therefore, snow blocks and ice can be naturally dropped in a shorter time, and snow and ice can be prevented from accumulating over time.
- "having an uneven shape on the surface” means that the surface of the film is photographed with a laser microscope and the calculated average height (Sa) is calculated when the average height in the region of 3.2 cm ⁇ 3.2 cm is calculated. ) Is 4 ⁇ m or more.
- the oil-containing layer is a layer in which an oil component is contained in a resin.
- the oil-containing layer is composed of a polymer component and an oil component.
- the polymer component forms a matrix, and the oil component is contained in this matrix.
- the polymer component is not particularly limited, but for example, silicone resin, polyurethane resin, polyurethane acrylic resin, vinyl chloride resin, polyester resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), acrylic resin, etc. Can be mentioned. Of these, a silicone resin is preferable from the viewpoint of excellent bleeding effect of the oil component and outdoor exposure durability.
- any suitable silicone resin can be adopted as long as the effects of the present invention are not impaired.
- the silicone resin may be of only one type or of two or more types.
- Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin.
- such a silicone resin may be a one-component silicone resin (for example, a one-component room temperature curable (RTV) resin) that is dried alone, or a two-component silicone resin (for example, a two-component silicone resin). It may be a two-component room-temperature curable (RTV) resin).
- silicone resin examples include commercially available one-component RTV rubbers manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-3423, KE-347, KE-3475, KE-3495). , KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-4988, KE-1820, KE-1825, KE-1831, KE-1833, KE.
- RTV rubbers manufactured by Shin-Etsu Chemical Co., Ltd.
- KE-3466 KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-41, KE-42, KE.
- Silicone rubber injection molding system (for example, KEG-2000-40A / B, KEG-2000-50A / B, KEG-2000-60A / B, KEG-2000-70A / B, KEG-2001-40A / B, KEG -2001-50A / B, KE-1950-10A / B, KE-1950-20A / B, KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950 -50A / B, KE-1950-60A / B, KE-1950-70A / B, KE-1935A / B, KE-1987A / B, KE-1988A / B, KE-2019-40A / B, KE-2019 -50A / B, KE-2019-60A / B, KE-2017-30A / B, KE-2017-40A / B, KE-2017-50A / B, KE-2090-40A / B,
- a two-component silicone resin is preferable from the viewpoint of phase separation from an oil component that bleeds on the surface at a predetermined temperature, and specifically, KE-1950-10A / B and KE-1950-20A / B. , KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950-50A / B, KE-1950-60A / B, KE-1950-70A / B, KE -1935A / B and the like are more preferable.
- the oil component is not particularly limited as long as it bleeds out to the surface of the film and has either a snow accretion prevention function or an icing prevention function (hereinafter, also referred to as a snow accretion prevention function). ..
- the oil component include silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil and the like. Of these, silicone oil is preferable from the viewpoint of snow accretion prevention effect and bleeding effect.
- the oil component one type may be used alone, or two or more types may be used in combination.
- silicone oil examples include silicone oil represented by the general formula (1).
- each of R 1 independently has an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a fluoroalkyl group, a polyether group, a carbinol group, an amino group, an epoxy group, and a silanol group. , Or a hydroxyl group, and n represents an integer from 0 to 150. A plurality of n may be the same or different.
- the R 1 in the general formula (1) is preferably an alkyl group, a phenyl group having 1 to 10 carbon atoms, a polyether group, a carbinol group, an amino group, an epoxy group.
- silicone oil represented by the general formula (1) examples include dimethyl silicone oil in which all of R 1 are methyl groups, and some of the methyl groups of these dimethyl silicone oils are replaced with phenyl groups.
- Phylmethyl silicone oil, polyether group-containing silicone oil substituted with polyether group, carbinol group-containing silicone oil substituted with carbinol group, amino group-containing silicone oil substituted with amino group, or epoxy group examples thereof include silicone oil containing an epoxy group substituted with.
- phenylmethyl silicone oil, polyether group-containing silicone oil, and carbinol group-containing silicone oil are preferable because they do not have reactivity or self-condensation with the silicone resin when the silicone resin is used as the polymer component.
- the silicone oil represented by the general formula (1) has a number average molecular weight of preferably 100 to 40,000, more preferably 200 to 20,000.
- the silicone oil has a viscosity at 25 ° C. of preferably 1 to 10000 cSt, more preferably 5 to 5000 cSt, still more preferably 8 to 1000 cSt, and particularly preferably 10 to 500 cSt.
- the viscosity at 25 ° C. is within the above range, the snow accretion / ice-sliding property is excellent, so that an excellent snow accretion / icing prevention effect can be obtained.
- silicone oil examples include silicone oil manufactured by Momentive Performance Materials Japan LLC (for example, TSF431, TSF433, TSF437, TSF451 series, etc.) and silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.
- TSF437 KF50 series, KF54 series, KF-6000, KF-6001, KF-6002, etc.
- KF96 series, TSF451 series and the like it is preferable to use in combination in order to improve the properties.
- examples of the fluorine oil include perfluoropolyether, perfluorodecalin, perfluorooctane and the like.
- Perfluoropolyether is preferred in terms of chemical stability.
- Examples of the perfluoropolyether include structural formulas: A- (C 3 F 6 O) x (CF 2 O) y (C 2 F 4 O) z- B (in the formula, the terminal group A is -F, -CF 3 , -C 2 F 5 , -C 3 F 7 , -CF (CF 3 ) OCF 3 , -OF, -OCF 3 , -OC 2 F 5 , -OC 3 F 7 , -OCF (CF 3 ) It is one of OCF 3 , and the terminal group B is any of -CF 3 , -C 2 F 5 , -C 3 F 7 , -CF (CF 3 ) OCF 3 , and x, y, z are 0.
- a compound which is a positive integer, x + y + z> 1, and has a viscosity at 25 ° C. of 50 to 500,000 cSt) can be mentioned.
- Specific examples of the perfluoropolyether include CF 3 O- (CF 2 CF (CF 3 ) O) x (CF 2 O) y- CF 3 (in the formula, x and y are as described above.
- the oil-containing layer may contain other components depending on the intended use as long as the effects of the present invention are not impaired.
- other components include solvents, liquid paraffins, surfactants, antibacterial agents, ultraviolet absorbers, fillers, cross-linking agents and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- solvent examples include ethyl acetate and liquid hydrocarbons such as hexane, heptane, benzene, toluene, xylene and 1-tetradecene.
- liquid paraffin for example, P-40, P-55, P-60, P-70, P-80, P-100, P-120, P- of MORESCO Co., Ltd., which can be obtained as commercial products.
- examples thereof include 150, P-200, P-260, P-350, and hydrocarbon-based liquid paraffin manufactured by Wako Pure Chemical Industries, Ltd.
- surfactant examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants and the like.
- anionic surfactants include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfo fatty acids or esters, alkane sulfonates, saturated or Examples thereof include unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid-type surfactants, N-acyl amino acid-type surfactants, alkyl or alkenyl phosphate esters or salts thereof.
- nonionic surfactant examples include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoside, fatty acid glycerin monoester, and alkyl.
- examples include amine oxides.
- amphoteric surfactant examples include a carboxy type or a sulfobetaine type amphoteric surfactant.
- cationic surfactant examples include a quaternary ammonium salt and the like.
- Antibacterial agents include, for example, azoxystrobin, benaraxil, benomil, bitertanol, bromconazole, captahole, captan, carbendazim, quinomethionate, chlorotalonyl, clozolinate, cyprodinyl, diclofluanide, diclofen, dichromedin, dichloran, dietofencarb.
- examples of natural antibacterial agents include Chinese herbs such as Moso bamboo extract, hinokitiol, garlic extract, and licorice.
- Inorganic antibacterial agents such as silver, copper, zinc, tin, lead and gold can also be mentioned. If necessary, zeolite, hydroxyapatite, calcium carbonate, silica gel, aluminum silicate calcium, polysiloxane compound, zirconium phosphate, zirconium sulfate, ion exchanger, zinc oxide and the like are used as carriers for these inorganic antibacterial agents. it can.
- Examples of the synthetic antibacterial agent include 2-pyridinethiol-1-oxide, p-chloro-m-cresol, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, benzisothiazolin, 5-.
- Examples thereof include chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2'-dithio-bis- (pyridin-1-oxide) and the like.
- UV absorbers examples include TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, and TINUVIN326 manufactured by BASF.
- the filler examples include silica particles and diatomaceous earth. Further, as the filler, particles having a hydrophobically treated surface are preferable from the viewpoint of dispersibility. Examples of such a surface treatment method include a method of surface treatment with dimethylpolysiloxane, dimethyldichlorosilane, hexamethylene disilazane, cyclic dimethylsiloxane, or the like.
- the size of the particles whose surface is hydrophobically treated is preferably an average particle size of 5 nm to 300 nm.
- cross-linking agent examples include isocyanate-based compounds, epoxy-based compounds, melamine-based compounds, metal chelate compounds, oxazoline-based compounds, aziridine-based compounds, and ethyleneimine.
- the lower limit of the content ratio of the polymer component with respect to the entire oil-containing layer is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and also.
- the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
- a method of heating and curing a resin composition in which the polymer component, the oil component, and other components are mixed if necessary can be mentioned.
- the polymer component forms a matrix, and the oil component is dispersed therein.
- the layer thickness of the oil-containing layer may be appropriately determined according to the intended use, but is preferably 0.05 to 3 mm (50 to 3000 ⁇ m).
- the thickness of the oil-containing layer is 0.05 mm or more, the durability against outdoor exposure is improved, and the amount of the oil component contained can be increased, so that the bleeding effect is enhanced and the snow accretion prevention function is improved. Can be made to.
- the layer thickness of the oil-containing layer is 3 mm or less, the handleability is improved.
- the lower limit of the layer thickness of the oil-containing layer is more preferably 0.075 mm or more, further preferably 0.1 mm or more, and the upper limit is more preferably 2.5 mm or less, still more preferably 2 mm or less.
- the bleeding temperature of the oil-containing layer can be appropriately set according to the usage environment so that the oil component bleeds at a predetermined temperature or lower. For example, when 0 ° C. is set to a predetermined temperature, the oil component that bleeds at 0 ° C. or lower can be appropriately selected and used to bleed the oil component from the film when the outside air becomes 0 ° C. or lower. it can.
- ⁇ Base material> In the film of the present invention, it is preferable to provide a base material in order to support the oil-containing layer and maintain the strength of the film.
- the material constituting the base material can be appropriately selected in consideration of the adhesiveness to the object, the strength of the entire product, etc.
- polyurethane resin polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, etc.
- silicone resin elastomers, fluororesin, polyamide resin, polyolefin resin (polyurethane, polypropylene, etc.), ionomer, polyethylene terephthalate resin and the like.
- polyester resin, ionomer, or polyethylene terephthalate resin from the viewpoint of stickability to an object.
- Such a base material layer may be only one kind or two or more kinds.
- the thickness of the base material may be appropriately determined according to the intended use, but is preferably, for example, 10 to 300 ⁇ m, more preferably 30 to 250 ⁇ m, and further preferably 50 to 200 ⁇ m.
- the film has an appropriate strength and is excellent in handleability.
- the film of the present invention is, for example, a method of forming a coating film using a resin composition containing a polymer component and an oil component, imparting irregularities to the surface of the coating film, and then curing the coating film. It can be manufactured by a method in which another member having unevenness is directly or indirectly installed on a cured coating film formed by using an object so that the cured coating film follows the unevenness of the other member.
- the method for producing a film of the present invention includes the following steps (a) and (b) or the following steps (c).
- (A) A step of forming a coating film using a resin composition containing a polymer component and an oil component to form an uneven shape on the surface of the coating film
- (b) The coating film on which the uneven shape is formed.
- Step of Curing A coating film is formed using a resin composition containing a polymer component and an oil component, and after the coating film is cured, a member having irregularities on the surface is formed on one surface of the cured coating film.
- the film of the present invention can be suitably produced by the above-mentioned production method.
- Step (a) In the step (a), first, a resin composition containing a polymer component and an oil component in an arbitrary ratio is prepared.
- the resin composition may contain other components as described above.
- the resin mixture is preferably stirred until the raw material components are uniform, and a stirrer may be used.
- air bubbles may be contained in the oil-containing layer after molding, in which case the film strength may be lowered or the product appearance may be deteriorated. It is preferable to perform punching.
- the degassing method include a method of defoaming for about several seconds to 5 minutes with a planetary stirrer and a method of depressurizing for about several seconds to 30 minutes under vacuum.
- the resin composition obtained as described above is applied onto a coating table or a base material to form a coating film (oil-containing layer).
- the coating method is not particularly limited as long as the coating film is applied so that the film thickness after drying is 0.05 to 3 mm, and examples thereof include a method of cast coating using an applicator and a method of brush coating. ..
- an uneven shape is formed on the surface of the coating film.
- the method of forming the uneven shape on the coating film include a method in which a roller having unevenness on the peripheral surface is brought into close contact with the coating film to transfer the unevenness to the coating film, and a punching sheet having unevenness on the surface is applied to the coating film.
- Examples thereof include a method of pressing to transfer the unevenness to the coating film, a method of pressing sandpaper having the unevenness on the surface onto the coating film, and transferring the unevenness to the coating film.
- the height of the unevenness can be appropriately adjusted by adjusting the pressing force of a processed member such as a roller or a punching sheet that imparts the uneven shape.
- Step (b) In the step (b), the coating film having the uneven shape obtained in the step (a) is cured.
- the curing method can be carried out by a conventionally known method, and examples thereof include a method of heating and drying, a method of curing by ultraviolet irradiation, and a method of adding a cross-linking agent. In the case of heat drying, it is preferable to heat at 100 to 160 ° C. for 1 to 300 minutes.
- Step (c) In the step (c), a coating film is first formed using a resin composition containing a polymer component and an oil component in an arbitrary ratio.
- the method for forming the coating film can be carried out in the same manner as in the above step (a).
- the curing method can be carried out by a conventionally known method, and examples thereof include a method of heating and drying, a method of curing by ultraviolet irradiation, and a method of adding a cross-linking agent.
- heat drying it is preferable to heat at 100 to 160 ° C. for 1 to 300 minutes.
- a member having irregularities on the surface is installed on one of the main surfaces.
- the member include an adhesive layer having irregularities on the surface (for example, a base material-less adhesive sheet), a substrate having irregularities on the surface, and the like.
- the film of the present invention can be obtained as described above.
- the thickness of the film of the present invention can be appropriately selected in the range of 0.06 to 3.5 mm in consideration of the desired strength of the film, the size of the object (structure) to which the film is applied, and the like.
- the calculated average height (Sa) of the region of 3.2 cm ⁇ 3.2 cm on the surface of the oil-containing layer of the film is 4 ⁇ m or more.
- the lower limit of the calculated average height (Sa) is preferably 4.3 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, and the upper limit is preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less. , 50 ⁇ m or less is more preferable.
- the calculated average height (Sa) is obtained by photographing the surface of the film with a laser microscope (for example, "OPTELICS HYBRID” manufactured by Lasertec) and calculating the average height in a region of 3.2 cm ⁇ 3.2 cm. be able to.
- a laser microscope for example, "OPTELICS HYBRID” manufactured by Lasertec
- the maximum pitch-to-pitch distance of the uneven shape is 2000 ⁇ m or more.
- the maximum pitch-to-pitch distance is 2000 ⁇ m or more, a sufficient uneven shape is formed on the film surface, so that the film has excellent snow-sliding properties.
- the maximum inter-pitch distance of the uneven shape is more preferably 2500 ⁇ m or more, and the upper limit is preferably 60,000 ⁇ m or less, more preferably 55,000 ⁇ m or less.
- the film of the present invention is used as a surface covering material by being provided on the surface of an object (structure).
- object any object exposed to the natural environment such as snowfall and wind and rain can be used without any particular restrictions.
- aircraft, railways, automobiles, wind power generators, houses, traffic lights, signs, etc. Can be mentioned.
- Example 1 The resin composition produced in Production Example 1 was uniformly applied onto a polyethylene terephthalate (PET) film (thickness: 125 ⁇ m) using an applicator so that the thickness of the oil-containing layer after drying was 150 ⁇ m. An unevenness was formed on the coating film by using a roller having an unevenness on the peripheral surface. Then, it was dried at 150 degreeC for 10 minutes to form an oil-containing layer, and the film of Example 1 was prepared. The surface of the film was photographed with a laser microscope (“OPTELICS HYBRID” manufactured by Lasertec), measurements were taken in an area of 3.2 cm ⁇ 3.2 cm, and the average height was calculated. The calculated average height (Sa) was 4. It was 4 ⁇ 1.0 ⁇ m.
- PTT polyethylene terephthalate
- Example 2 A film of Example 2 was produced in the same manner as in Example 1 except that irregularities were formed on the coating film using a punching sheet.
- the calculated average height (Sa) of the film surface was 15.9 ⁇ 6.1 ⁇ m.
- Example 3 A film of Example 3 was produced in the same manner as in Example 1 except that a roller different from that of Example 1 was used.
- the calculated average height (Sa) of the film surface was 20.9 ⁇ 3.3 ⁇ m.
- Example 4 A film of Example 4 was produced in the same manner as in Example 1 except that a roller different from that of Example 1 was used.
- the calculated average height (Sa) of the film surface was 21.4 ⁇ 5.3 ⁇ m.
- Example 5 A film of Example 5 was produced in the same manner as in Example 2 except that a punching sheet different from that of Example 2 was used.
- the calculated average height (Sa) of the film surface was 24.9 ⁇ 5.0 ⁇ m.
- Example 6 A film of Example 6 was produced in the same manner as in Example 1 except that a roller different from that of Example 1 was used.
- the calculated average height (Sa) of the film surface was 26.1 ⁇ 5.2 ⁇ m.
- Example 7 A film of Example 7 was produced in the same manner as in Example 1 except that a roller different from that of Example 1 was used.
- the calculated average height (Sa) of the film surface was 30.3 ⁇ 6.1 ⁇ m.
- Example 8 A film of Example 8 was produced in the same manner as in Example 1 except that a roller different from that of Example 1 was used.
- the calculated average height (Sa) of the film surface was 46.2 ⁇ 10.2 ⁇ m.
- Example 9 The resin composition produced in Production Example 1 was uniformly applied onto a polyethylene terephthalate (PET) film (thickness: 125 ⁇ m) using an applicator so that the thickness of the oil-containing layer after drying was 150 ⁇ m.
- the oil-containing layer was formed by drying at 150 ° C. for 10 minutes.
- an adhesive having a concavo-convex shape with a minimum pitch distance of 1500 ⁇ m and a maximum pitch distance of 5000 ⁇ m was placed on the substrate surface of the film to prepare the film of Example 9.
- the calculated average height (Sa) of the film surface was 8.7 ⁇ 2.8 ⁇ m.
- Comparative Example 1 The resin composition produced in Production Example 1 was uniformly applied onto a polyethylene terephthalate (PET) film (thickness: 125 ⁇ m) using an applicator so that the thickness of the oil-containing layer after drying was 150 ⁇ m. The film was dried at 150 ° C. for 10 minutes to form an oil-containing layer to prepare a film of Comparative Example 1. The calculated average height (Sa) of the film surface was 3.4 ⁇ 1.2 ⁇ m.
- PET polyethylene terephthalate
- Comparative Example 2 A film of Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that the resin composition prepared in Production Example 2 was used.
- the calculated average height (Sa) of the film surface was 4.1 ⁇ 0.5 ⁇ m.
- Comparative Example 4 A film of Comparative Example 4 was produced in the same manner as in Comparative Example 3 except that a roller different from that of Comparative Example 3 was used.
- the calculated average height (Sa) of the film surface was 29.9 ⁇ 4.6 ⁇ m.
- Comparative Example 5 A film of Comparative Example 5 was produced in the same manner as in Comparative Example 3 except that a roller different from that of Comparative Example 3 was used.
- the calculated average height (Sa) of the film surface was 32.2 ⁇ 2.1 ⁇ m.
- Comparative Example 1 is a film having an oil-containing layer on the film surface and not having an uneven shape
- Comparative Examples 2 to 5 are examples in which the film surface is composed of a non-oil-containing layer
- Comparative Examples 3 to 5 are examples. It has an uneven shape.
- Comparative Example 1 had a shorter snow accretion time than Comparative Examples 2 to 5, but Examples 1 to 9 had a significantly shorter snow accretion time than Comparative Example 1, and the snow mass could be naturally dropped in a shorter time. It was found that it had an excellent snow accretion and icing prevention effect.
- the film of the present invention is useful for preventing snow and ice from adhering to the surfaces of aircraft, railroads, automobiles, wind power generators, houses, traffic lights, signs, and the like.
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Abstract
Description
(a)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜の表面に凹凸形状を形成する工程
(b)前記凹凸形状が形成された前記塗膜を硬化させる工程
(c)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜を硬化させた後、表面に凹凸を有する部材を硬化塗膜の一方の面に設置して塗膜表面に凹凸形状を形成する工程
なお、本発明において、「フィルム」とは、JIS K 6900:1994の定義におけるフィルムとシートを含む意味である。JIS K 6900:1994での定義では、フィルムとは長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通例ロールの形で供給されるものをいい、シートとは薄く、一般にその厚さが長さと幅の割には小さい平らな製品をいう。フィルムとシートの境界は定かではなく、本明細書においてフィルムにはシートの概念も含まれるものとする。
また、本明細書において、「質量」は「重量」と同義である。
本発明において、「表面に凹凸形状を備える」とは、レーザー顕微鏡によりフィルムの表面を撮影し、3.2cm×3.2cmの領域における平均高さを算出した際に、算出平均高さ(Sa)が4μm以上となるものである。
オイル含有層は、オイル成分が樹脂中に含有されてなる層である。オイル含有層は、ポリマー成分とオイル成分とを含有して構成される。ポリマー成分がマトリックスを形成し、このマトリックス中にオイル成分が含有される。
ポリマー成分としては、特に制限されないが、例えば、シリコーン樹脂、ポリウレタン樹脂、ポリウレタンアクリル樹脂、塩化ビニル樹脂、ポリエステル樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂(ポリエチレン、ポリプロピレン等)、アクリル樹脂等が挙げられる。中でもオイル成分のブリード効果並びに屋外曝露耐久性に優れるという観点から、シリコーン樹脂が好ましい。
これらの中でも、所定温度で表面にブリードするオイル成分との相分離性の観点から、2液型のシリコーン樹脂が好ましく、具体的に、KE-1950-10A/B、KE-1950-20A/B、KE-1950-30A/B、KE-1950-35A/B、KE-1950-40A/B、KE-1950-50A/B、KE-1950-60A/B、KE-1950-70A/B、KE-1935A/B等がより好ましい。
オイル成分は、フィルムの表面にブリードアウトし、かつ着雪防止機能及び着氷防止機能のうちのいずれか一方(以下、着雪着氷防止機能ともいう。)を有するものであればとくに制限されない。オイル成分としては、例えば、シリコーンオイル、フッ素オイル、炭化水素系オイル、ポリエーテル系オイル、エステル系オイル、リン化合物系オイル、鉱油系オイル等が挙げられる。中でも着雪着氷防止効果およびブリード効果の観点から、シリコーンオイルが好ましい。オイル成分は、1種を単独で用いてもよいし、2種以上を組み合せて用いてもよい。
これらの中でも、ポリマー成分との相分離性の観点から、TSF437、KF50シリーズ、KF54シリーズ、KF-6000、KF-6001、KF-6002等を用いることが好ましく、これらオイル成分のポリマー成分との親和性を高めるために、KF96シリーズ、TSF451シリーズ等を併用することがより好ましい。
また、オイル含有層には、本発明の効果を損なわない範囲で用途に応じてその他の成分を含有させてもよい。その他の成分としては、例えば、溶剤、流動パラフィン、界面活性剤、抗菌剤、紫外線吸収剤、フィラー、架橋剤等が挙げられる。これらは、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
アニオン系界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルまたはアルケニルエーテル硫酸塩、アルキルまたはアルケニル硫酸塩、α-オレフィンスルホン酸塩、α-スルホ脂肪酸またはエステル塩、アルカンスルホン酸塩、飽和または不飽和脂肪酸塩、アルキルまたはアルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、N-アシルアミノ酸型界面活性剤、アルキルまたはアルケニルリン酸エステルまたはその塩等が挙げられる。ノニオン系界面活性剤としては、例えば、ポリオキシアルキレンアルキルまたはアルケニルエーテル、ポリオキシエチレンアルキルフェニルエーテル、高級脂肪酸アルカノールアミドまたはそのアルキレンオキサイド付加物、ショ糖脂肪酸エステル、アルキルグリコシド、脂肪酸グリセリンモノエステル、アルキルアミンオキサイド等が挙げられる。両性界面活性剤としては、例えば、カルボキシ型またはスルホベタイン型両性界面活性剤等が挙げられる。カチオン系界面活性剤としては、例えば、第4級アンモニウム塩等が挙げられる。
本発明のフィルムは、オイル含有層を支持し、フィルムの強度を保つために、基材を設けることが好ましい。
本発明のフィルムは、例えば、ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、該塗膜の表面に凹凸を付与した後に塗膜を硬化させる方法、前記樹脂組成物を用いて形成した硬化塗膜に、凹凸を有する他の部材を直接又は間接的に設置して、前記硬化塗膜に他の部材の凹凸を追随させる方法等により製造できる。
(a)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜の表面に凹凸形状を形成する工程
(b)前記凹凸形状が形成された前記塗膜を硬化させる工程
(c)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜を硬化させた後、表面に凹凸を有する部材を硬化塗膜の一方の面に設置して塗膜表面に凹凸形状を形成する工程
本発明のフィルムは上記製造方法により好適に製造できる。
工程(a)では、まず、ポリマー成分とオイル成分とを任意の割合で含有した樹脂組成物を作製する。樹脂組成物には、上記したようなその他の成分を含有していてもよい。樹脂混合物は、原料成分が均一になるまで撹拌することが好ましく、撹拌機を使用してもよい。
工程(b)では、工程(a)で得られた凹凸形状が形成された塗膜を硬化させる。硬化の方法は、従来公知の方法で行うことができ、例えば、加熱乾燥する方法、紫外線照射により硬化する方法、架橋剤を添加する方法等が挙げられる。
加熱乾燥する場合、100~160℃で1~300分加熱するのが好ましい。
工程(c)では、初めにポリマー成分とオイル成分とを任意の割合で含有した樹脂組成物を用いて塗膜を形成する。塗膜の形成方法は、前記工程(a)と同様にして行うことができる。
加熱乾燥する場合、100~160℃で1~300分加熱するのが好ましい。
なお、算出平均高さ(Sa)は、レーザー顕微鏡(例えば、レーザーテック製「OPTELICS HYBRID」)によりフィルムの表面を撮影し、3.2cm×3.2cmの領域における平均高さを算出することにより求めることができる。
なお、実施例、比較例中、「部」とあるのは質量基準を意味する。
KE-1950-50AとKE-1950-50Bを質量比1:1で混合したシリコーン樹脂(いずれも信越化学工業株式会社製、2液型RTVゴム)50部、KF-96-50cs(信越化学工業株式会社製シリコーンオイル)30部、TSF-437(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーンオイル)20部を、均一に撹拌混合して、樹脂組成物を作製した。
KE-1950-50AとKE-1950-50Bを質量比1:1で混合したシリコーン樹脂(いずれも信越化学工業株式会社製、2液型RTVゴム)50部、酢酸エチル(富士フィルム和光純薬製)50部を均一に撹拌混合して、樹脂組成物を作製した。
製造例1で作製した樹脂組成物を、ポリエチレンテレフタレート(PET)製フィルム(膜厚125μm)上に、乾燥後のオイル含有層の厚さが150μmになるようにアプリケーターを用いて均一に塗布した。周面に凹凸を有するローラーを用いて、塗膜に凹凸を形成した。その後、150℃で10分乾燥させてオイル含有層を形成して、実施例1のフィルムを作製した。
レーザー顕微鏡(レーザーテック製「OPTELICS HYBRID」)によりフィルムの表面を撮影し、3.2cm×3.2cmの領域において測定を行い、平均高さを算出したところ、算出平均高さ(Sa)は4.4±1.0μmであった。
パンチングシートを用いて塗膜に凹凸を形成した以外は実施例1と同様にして実施例2のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は15.9±6.1μmであった。
実施例1とは異なるローラーを用いた以外は、実施例1と同様にして実施例3のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は20.9±3.3μmであった。
実施例1とは異なるローラーを用いた以外は、実施例1と同様にして実施例4のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は21.4±5.3μmであった。
実施例2とは異なるパンチングシートを用いた以外は、実施例2と同様にして実施例5のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は24.9±5.0μmであった。
実施例1とは異なるローラーを用いた以外は、実施例1と同様にして実施例6のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は26.1±5.2μmであった。
実施例1とは異なるローラーを用いた以外は、実施例1と同様にして実施例7のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は30.3±6.1μmであった。
実施例1とは異なるローラーを用いた以外は、実施例1と同様にして実施例8のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は46.2±10.2μmであった。
製造例1で作製した樹脂組成物を、ポリエチレンテレフタレート(PET)製フィルム(膜厚125μm)上に、乾燥後のオイル含有層の厚さが150μmになるようにアプリケーターを用いて均一に塗布し、150℃で10分乾燥させてオイル含有層を形成した。その後、フィルムの基材面に、最小ピッチ間距離が1500μm、最大ピッチ間距離が5000μmの凹凸形状を有する粘着剤を設置して、実施例9のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は8.7±2.8μmであった。
製造例1で作製した樹脂組成物を、ポリエチレンテレフタレート(PET)製フィルム(膜厚125μm)上に、乾燥後のオイル含有層の厚さが150μmになるようにアプリケーターを用いて均一に塗布し、150℃で10分乾燥させてオイル含有層を形成して、比較例1のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は3.4±1.2μmであった。
製造例2で作製した樹脂組成物を用いた以外は比較例1と同様にして比較例2のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は4.1±0.5μmであった。
製造例2で作製した樹脂組成物を、ポリエチレンテレフタレート(PET)製フィルム(膜厚125μm)上に、乾燥後のオイル含有層の厚さが150μmになるようにアプリケーターを用いて均一に塗布した。周面に凹凸を有するローラーを用いて、塗膜に凹凸を形成した。その後、150℃で10分乾燥させてオイル含有層を形成して、比較例3のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は20.4±7.0μmであった。
比較例3とは異なるローラーを用いた以外は、比較例3と同様にして比較例4のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は29.9±4.6μmであった。
比較例3とは異なるローラーを用いた以外は、比較例3と同様にして比較例5のフィルムを作製した。フィルム表面の算出平均高さ(Sa)は32.2±2.1μmであった。
各例で作製したフィルムを縦10cm×横10cm(面積100cm2)の大きさにカットし、縦10cm×横10cm(面積100cm2)のアクリル板にオイル含有層が表面となるように貼着し、環境温度を1℃に設定した試験室内に設置した。水平に設置したフィルム表面に対して湿り雪の雪塊を約20g付着させた。雪塊を付着させたアクリル板を床面に対し60°傾けて設置した。
その後、雪塊が落下するまでの時間(滑雪時間)を測定した。結果を表1に示す。
Claims (6)
- オイル成分を樹脂中に含有するオイル含有層を最外層として含み、前記オイル成分は所定温度以下において前記オイル含有層の表面からブリードし、前記オイル含有層の前記表面が凹凸形状を備え、
前記オイル含有層の前記表面における3.2cm×3.2cmの領域における算出平均高さ(Sa)が4μm以上である、フィルム。 - 前記算出平均高さ(Sa)が10μm以上である、請求項1に記載のフィルム。
- 前記凹凸形状の最大ピッチ間距離が2000μm以上である、請求項1または2に記載のフィルム。
- 対象物の表面に雪や氷が経時堆積するのを防止する、請求項1~3のいずれか1項に記載のフィルム。
- 以下の(a)及び(b)の工程、又は(c)の工程を含む、フィルムの製造方法。
(a)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜の表面に凹凸形状を形成する工程
(b)前記凹凸形状が形成された前記塗膜を硬化させる工程
(c)ポリマー成分とオイル成分とを含有する樹脂組成物を用いて塗膜を形成し、前記塗膜を硬化させた後、表面に凹凸を有する部材を硬化塗膜の一方の面に設置して塗膜表面に凹凸形状を形成する工程 - 前記製造方法が、請求項1~4のいずれか1項に記載のフィルムを製造する方法である、請求項5に記載のフィルムの製造方法。
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DE102020007632A1 (de) | 2020-12-14 | 2022-06-15 | Giesecke+Devrient Currency Technology Gmbh | Verfahren zur Aufbringung von geprägten Strukturen auf eine Oberfläche eines Objekts |
WO2022202721A1 (ja) * | 2021-03-26 | 2022-09-29 | 日東電工株式会社 | 塗料 |
WO2023190417A1 (ja) * | 2022-03-28 | 2023-10-05 | 日東電工株式会社 | シート体 |
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