阅读说明：本技术 膜 (Film ) 是由 松隈大辅 小名遥 中村吉宏 藤田浩之 于 2020-03-13 设计创作，主要内容包括：本发明的目的在于提供能够提高滑雪性、从而实现对结构体优异的防积雪和/或结冰的膜。本发明的膜包含在树脂中含有油成分的含油层作为最外层,所述油成分在给定温度以下从所述含油层表面渗出,所述含油层的所述表面具备凹凸形状,其中,在所述含油层的所述表面的3.2cm×3.2cm区域内的算术平均高度(Sa)为4μm以上。(The purpose of the present invention is to provide a film that can improve skiing performance and thereby achieve excellent snow and/or ice protection for a structure. The film of the present invention comprises, as an outermost layer, an oil-containing layer containing an oil component in a resin, the oil component exuding from a surface of the oil-containing layer at a given temperature or lower, the surface of the oil-containing layer having a concavo-convex shape, wherein an arithmetic average height (Sa) in a region of 3.2cm × 3.2cm of the surface of the oil-containing layer is 4 μm or more.)

1. A film comprising an oil-containing layer containing an oil component in a resin as an outermost layer, the oil component exuding from a surface of the oil-containing layer at a given temperature or lower, the surface of the oil-containing layer being provided with a concavo-convex shape,

wherein an arithmetic mean height (Sa) in a 3.2cm by 3.2cm region of said surface of said oil-containing layer is 4 μm or more.

2. The film of claim 1, wherein,

the arithmetic average height (Sa) is 10 [ mu ] m or more.

3. The film according to claim 1 or 2,

the maximum distance between undulations of the concave-convex shape is 2000 [ mu ] m or more.

4. A film according to any one of claims 1 to 3, which prevents the deposition of snow or ice on the surface of an object over time.

5. A method for producing a film, which comprises the following steps (a) and (b), or comprises the step (c):

(a) forming a coating film using a resin composition containing a polymer component and an oil component, and forming a concavo-convex shape on the surface of the coating film;

(b) curing the coating film having the uneven shape formed thereon;

(c) and forming a coating film using a resin composition containing a polymer component and an oil component, and after curing the coating film, providing a member having irregularities on the surface thereof on one surface of the cured coating film to form irregularities on the surface of the coating film.

6. The method for producing a film according to claim 5, which is a method for producing the film according to any one of claims 1 to 4.

Technical Field

The present invention relates to a film, and more particularly, to a film used as a surface coating material for preventing snow and ice from adhering to the surface of an object such as an airplane, a railway, an automobile, a wind turbine, a house, a signal light, a signboard, and the like.

Background

Ice adhesion (freezing) to the surface of an object and snow adhesion (snow accumulation) due to snowfall have been causes of damage or obstacles in various fields. For example, icing on aircraft wings, snow/freezing under the aircraft, snow on car headlights, icing on wind turbine blades, snow/freezing on signal lights, etc. may all be obstacles to their operation, safety, etc. Further, snow accumulation and freezing on house roofs, signboards, and the like may cause damage to these structures or damage to people due to snow fall.

In order to avoid such damage or obstacle, various measures for protecting the structure from snow have been studied, and for example, various films and sheets having a snow-hard function and a ski function have been proposed.

For example, patent document 1 proposes a ski-friendly solid body in which a plurality of grooves extending in one direction are provided in at least a part of the surface of the solid body to form irregularities at intervals of 2 μm or more and 4 μm or less, and the convex portions of the irregularities are made hydrophilic at a water contact angle of 30 ° or less, and the concave portions are made water-repellent at a water contact angle of 90 ° or more.

Patent document 2 proposes a snow-hard/snowboard film or sheet having a water-repellent surface and having an uneven shape formed by alternately arranging top portions formed in a linear shape in a predetermined direction and recessed portions formed in a linear shape in the predetermined direction at positions lower than the top portions and adjacent to the top portions, wherein at least a part of the surface extending between the top portions adjacent to each other with the recessed portions interposed therebetween has a curved surface curved in a concave shape in a direction perpendicular to the predetermined direction.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2003-226867

Patent document 2: japanese patent laid-open publication No. 2018-162553

Disclosure of Invention

Problems to be solved by the invention

Although the effect of removing snow and ice on the surface of the structure by the film or sheet having the skiing function as described above can be expected, the amount of snow deposited on the structure increases as the amount of snow falling per unit time increases, and natural skiing in a shorter time is desired, and further improvement in skiing performance is 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 which can improve skiing performance and thereby realize excellent snow and/or ice prevention for a structural body.

Means for solving the problems

As a result of intensive studies, the present inventors have found that the above problems can be solved by forming a film surface with an oil-containing layer that causes oil to bleed at a predetermined temperature or lower and providing the surface with irregularities, and have completed the present invention.

That is, the present invention provides a film comprising an oil-containing layer containing an oil component in a resin as an outermost layer, the oil component exuding from a surface of the oil-containing layer at or below a predetermined temperature, the surface of the oil-containing layer having a concavo-convex shape, wherein an arithmetic average height (Sa) in a region of 3.2cm × 3.2cm of the surface of the oil-containing layer is 4 μm or more.

In a preferred embodiment of the film, the arithmetic average height (Sa) is preferably 10 μm or more.

In a preferred embodiment of the film, the maximum pitch of the uneven shape is preferably 2000 μm or more.

In a preferred embodiment of the film, the film is preferably a film for preventing snow or ice from depositing on the surface of the object over time.

The present invention also provides a method for producing a film, the method including the following steps (a) and (b), or including the step (c):

(a) forming a coating film using a resin composition containing a polymer component and an oil component, and forming a concavo-convex shape on the surface of the coating film;

(b) curing the coating film having the uneven shape formed thereon;

(c) and forming a coating film using a resin composition containing a polymer component and an oil component, and curing the coating film, and then providing a member having irregularities on the surface thereof on one surface of the cured coating film to form irregularities on the surface of the coating film.

ADVANTAGEOUS EFFECTS OF INVENTION

In the film of the present invention, since the surface of the film is formed of an oil-containing layer containing an oil component that bleeds out at a given temperature or lower and the surface is provided with irregularities, the skiing performance can be improved, and snow mass and ice adhering to the structure can naturally fall down in a shorter time.

Detailed Description

Hereinafter, embodiments of the present invention will be described in more detail, but the present invention is not limited to the embodiments described below at all.

In the present invention, the term "film" is used to mean a film or sheet including those defined in JIS K6900: 1994. In the definition of JIS K6900: 1994, a film refers to a thin flat product having an extremely small thickness compared with the length and width and a maximum thickness arbitrarily defined, and is usually fed in a roll form, and a sheet refers to a thin flat product having a thickness usually smaller than the length and width. There is no definite boundary between the film and the sheet, and in this specification, the film also includes the concept of the sheet.

In the present specification, "mass" and "weight" have the same meaning.

The film of the present invention comprises an oil-containing layer containing an oil component in a resin as an outermost layer, and the surface of the oil-containing layer has a concavo-convex shape. The oil component exudes from the surface of the oil-containing layer below a given temperature and coats the film surface. The film of the present invention has such a structure, and thus, snow or ice attached to the surface of the film is not directly contacted with the film, so that the friction force is reduced, the film is easily dropped by its own weight, and the sliding property of the film surface is further improved by the oil component leaked out. Therefore, the snow lump and ice can be naturally dropped in a shorter time, thereby preventing the deposition of the snow and ice over time.

In the present invention, the phrase "the surface has an uneven shape" means that when the surface of the film is photographed by a laser microscope and the average height in a region of 3.2cm × 3.2cm is calculated, the arithmetic average height (Sa) is 4 μm or more.

< oil-containing layer >

The oil-containing layer is a layer in which an oil component is contained in the resin. The oil-containing layer is composed of a polymer component and an oil component. The polymer component forms a matrix that contains the oil component.

(Polymer component)

The polymer component is not particularly limited, and examples thereof include: silicone resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and the like. Among them, silicone resins are preferred from the viewpoint of excellent bleeding effects of oil components and outdoor exposure durability.

As the silicone resin, any suitable silicone resin may be employed within a range not impairing the effects of the present invention. The silicone resin may be one kind only, or two or more kinds. The silicone resin may be a condensation type silicone resin or an addition type silicone resin. The silicone resin may be a one-pack type silicone resin dried alone (for example, a one-pack type room temperature curable (RTV) resin) or a two-pack type silicone resin (for example, a two-pack type room temperature curable (RTV) resin).

As the silicone resin, specifically, as silicone resins that can be obtained as commercially available products, for example: one-component RTV rubber (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-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE-1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-66, KE-67, 186-342, KE-347, KE-3491, KE-343417, KE-3427, KE-343418, KE-3434127, KE-3427, KE-349, KE-3480, KE-3494, KE-3480, KE-342, KE-347, KE-3491, KE-3434192, KE-3427, KE-349, and so as described in the present disclosure, KE-41, KE-42, KE-44, KE-45, KE-441, KE-445, KE-45S, etc.), two-component type RTV rubbers manufactured by shin-Etsu chemical industries, Ltd (e.g., KE-1800T-A/B, KE-66, KE-1031-A/B, KE-200, KE-118, KE-103, KE-108, KE-119, KE-109E-A/B, KE-1051J-A/B, KE-1012-A/B, KE-106, KE-1282-A/B, KE-1283-A/B, KE-1800-A/B/C, KE-1801-A/B/C, KE-1802-A/B/C, etc.), KE-1281-A/B, KE-1204-A/B, KE-1204-AL/BL, KE-1280-A/B, KE-513-A/B, KE-521-A/B, KE-1285-A/B, KE-1861-A/B, KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416, KE-1417, KE-1300T, KE-1310ST, KE-1314-2, KE-1316, KE-1600, KE-1603-A/B, KE-1606, KE-1222-A/B, KE-1241, etc.), silicone manufactured by CRS (TM)), KE-42AS, KE-420, KE-450, etc.), rubber compounds produced by shin-Etsu chemical industries, Ltd (for example, KE-655-U, KE-675-U, KE-931-U, KE-941-U, KE-951-U, KE-961-U, KE-971-U, KE-981-U, KE-961T-U, KE-971T-U, KE-871C-U, KE-9410-U, KE-9510-U, KE-9610-U, KE-9710-U, KE-U, KE-752-U, KE-762-U, KE-U, KE-782-U, KE-850-U, KE-870-U), KE-880-U, KE-890-U, KE-9590-U, KE-5590-U, KE-552-U, KE-582-U, KE-552B-U, KE-555-U, KE-575-U, KE-541-U, KE-551-U, KE-561-U, KE-571-U, KE-581-U, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551-U, KE-1571-U, KE-152-U, KE-174-U, KE-3601SB-U, KE-3711-U, KE-3801M-U, KE-5612G-U, KE-5620BL-U, KE-5620W-U, KE-5634-U, KE-7511-U, KE-7611-U, KE-765-U, KE-785-U, KE-7008-U, KE-7005-U, KE-503-U, KE-5042-U, KE-505-U, KE-6801-U, KE-136Y-U, LIMS (liquid silicone rubber injection molding System) manufactured by shin-Etsu chemical industries, Ltd (for example, KEG-2000-40A/B, KEG-2000-50A/B, KEG-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, KE-2090-50A/B, KE-2090-60A/B, KE-2090-70A/B, KE-2096-40A/B, KE-2096-50A/B, KE-2096-60A/B, etc.), LR7665 series manufactured by Asahi Kawakker Silicone Kaishiki, LR3033 series manufactured by Asahi Kawakker Silicone Kaishi, TSE3032 series manufactured by Meiji, Sylgard 184 manufactured by Dow Corning Tokyo Li.

Of these resins, a two-component type silicone resin is preferable from the viewpoint of phase separation from the oil component exuded to the surface at a given temperature, and specifically, 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 and the like are more preferable.

(oil component)

The oil component is not particularly limited as long as it has any one of the snow accumulation preventing function and the anti-icing function (hereinafter, also referred to as the snow accumulation preventing function) by bleeding out to the surface of the film. Examples of the oil component include: silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, etc. Among these, silicone oil is preferable from the viewpoint of the anti-icing effect and the bleeding effect. The oil component may be used alone or in combination of two or more.

Examples of the silicone oil include those represented by the general formula (1).

[ chemical formula 1]

In the general formula (1), R₁Each independently represents 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, a silanol group, or a hydroxyl group, and n represents an integer of 0 to 150. The plurality of n may be the same or different.

As R in the general formula (1)₁Preferably, the alkyl group has 1 to 10 carbon atoms, a phenyl group, a polyether group, a carbinol group, an amino group, or an epoxy group.

Specific examples of the silicone oil represented by the general formula (1) include R₁Dimethyl silicone oil containing all methyl groups, phenyl methyl silicone oil in which a part of the methyl groups of these dimethyl silicone oils is substituted with phenyl groups, polyether group-containing silicone oil substituted with polyether groups, carbinol group-containing silicone oil substituted with carbinol groups, amino group-containing silicone oil substituted with amino groups, epoxy group-containing silicone oil substituted with epoxy groups, and the like. Among these, phenyl methyl silicone oil, polyether group-containing silicone oil, and methanol group-containing silicone oil are preferable because they do not have reactivity and self-condensation with a silicone resin when a silicone resin is used as a polymer component.

The number average molecular weight of the silicone oil represented by the general formula (1) is preferably 100 to 40000, more preferably 200 to 20000.

The viscosity of the silicone oil at 25 ℃ is preferably 1 to 10000cSt, more preferably 5 to 5000cSt, still more preferably 8 to 1000cSt, and particularly preferably 10 to 500 cSt. When the viscosity at 25 ℃ is in the above range, excellent snow and ice accumulation preventing effect can be obtained because of excellent skiing/skating properties.

Specific examples of the silicone oil include: silicone oils manufactured BY Megaku corporation of Japan, such as TSF431, TSF433, TSF437, TSF451 series, silicone oils manufactured BY shin-Etsu chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF-6000, KF-6001, KF-6002, KF-6003, X-22-4039, PAM-E, KF-8010, KF-8012, KF-8008, KF-4917, X-22-163, etc.), silicone oils manufactured BY Dow Corning Tokyo Li corporation (for example, BY16-846 series, BY 8416 series, SH200 series, SH203 series, SH230 series, SF8419 series, SH5 series, SH550 series, SH 126510 series, SH 126710, Fw-16 series, Fw 220201 series, AK series, AKF series, L series, W series, AP series, AR series, AS series), and the like.

Among these silicone oils, TSF437, KF50 series, KF54 series, KF-6000 series, KF-6001, KF-6002 and the like are preferably used from the viewpoint of phase-separating property from the polymer component, and KF96 series, TSF451 series and the like are more preferably used in combination in order to improve the affinity of these oil components with the polymer component.

Further, as the fluorine oil, for example: perfluoropolyethers, perfluorodecalin, perfluorooctane, and the like. In terms of chemical stability, perfluoropolyether is preferred. Examples of perfluoropolyethers include those of the formula A- (C)₃F₆O)_x(CF₂O)_y(C₂F₄O)_z-B (in the formula, the terminal group A is-F, -CF₃、-C₂F₅、-C₃F₇、-CF(CF₃)OCF₃、-OF、-OCF₃、-OC₂F₅、-OC₃F₇、-OCF(CF₃)OCF₃The terminal group B is-CF₃、-C₂F₅、-C₃F₇、-CF(CF₃)OCF₃X, y, and z are 0 or a positive integer, and x + y + z > 1, and has a viscosity of 50 to 500000cSt at 25 ℃. Specific examples of the perfluoropolyether include: CF (compact flash)₃O-(CF₂CF(CF₃)O)_x(CF₂O)_y-CF₃(wherein x and y are as defined above), CF₃O-(CF₂O)_y(C₂F₄O)_z-CF₃(wherein y and z are as defined above), CF₃O-(CF₂CF(CF₃)O)_x-CF₃(wherein x is as defined above), and F- (CF)₂CF₂CF₂O)_x-C₂F₅(wherein x is as defined above) and the like。

(other Components)

In addition, other components may be contained in the oil-containing layer depending on the use within a range not impairing the effect of the present invention. Examples of other components include: solvents, liquid paraffin, surfactants, antibacterial agents, ultraviolet absorbers, fillers, crosslinking agents, and the like. These may be used alone or in combination of two or more.

Examples of the solvent include: and liquid hydrocarbons such as ethyl acetate, hexane, heptane, benzene, toluene, xylene, and 1-tetradecene.

As the liquid paraffin, for example, liquid paraffin that can be obtained as a commercially available product includes: p-40, P-55, P-60, P-70, P-80, P-100, P-120, P-150, P-200, P-260, P-350 manufactured by MORESCO, and hydrocarbon liquid paraffin manufactured by Wako pure chemical industries, Ltd.

Examples of the surfactant include: anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and the like.

Examples of the anionic surfactant include: alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α -olefin sulfonate, α -sulfo fatty acid or ester salt, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl or alkenyl phosphate or salt thereof, and the like. Examples of the nonionic surfactant include: polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, fatty acid monoglycerides, and alkylamine oxides. Examples of the amphoteric surfactant include a carboxyl-type amphoteric surfactant and a sulfobetaine-type amphoteric surfactant. Examples of the cationic surfactant include quaternary ammonium salts.

Examples of the antibacterial agent include: azoxystrobin, benalaxyl, benomyl, bitertanol, bromuconazole, captafol, captan and carbendazimCarbendazim, chlorfenapyr, chlorothalonil, ethirimol, cyprodinil, dichlorphenol, pyridaben, niclosamide, diethofencarb, dimethomorph, diniconazole, dithianon, epoxiconazole, prochloraz, fenoxanil, fluazinam, prochloraz, and the,Pyraclostrobin, fenarimol, fenbuconazole, difuramide, fenpiclonil, fentin, fluazinam, fludioxonil, dichlorflutolide, fluquinconazole, flusulfamide, flutolanil, hexachlorobenzene, hexaconazole, imibenconazole, ipconazole, iprodione, kresoxim-methyl, mancozeb, maneb, mepanipyrim, basidinin, metconazole, metiram, nickel bis (dimethyldithiocarbamate), fluoropyrimidinol, oxine-copper, fluazinam, thim, fluazinam, thi, fluazinam, thi, thitriax, thi, thitriafol,Quinate, pencycuron, tetrachlorophthalide, procymidone, methyl zineb, quintozene, sulfur, tebuconazole, phyllo phthalide, tetrazonitrobenzene, thifluzamide, thiophanate-methyl, carbosulfan, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, imidazosin, azinam, triticonazole, vinclozolin, zineb, ziram and the like. Examples of natural antibacterial agents include: traditional Chinese medicine components such as Phyllostachys Pubescens extract, hinokitiol, garlic extract, liquorice and the like. Further, there may be mentioned: inorganic antibacterial agents such as silver, copper, zinc, tin, lead, gold, etc. As the carrier of these inorganic antibacterial agents, zeolite, hydroxyapatite, calcium carbonate, silica gel, calcium aluminum silicate, polysiloxane compound, zirconium phosphate, zirconium sulfate, ion exchanger, zinc oxide, and the like can be used as necessary. Examples of the antibacterial agent of the composition include: 2-mercaptopyridine-1-oxide, p-chloro-m-cresol, polyhexamethylene biguanide hydrochloride, benzethonium chloride, alkylpolyaminoethyl glycine, benzisothiazoline, 5-chloro-2-methyl-4-isothiazolin-3-one, 1, 2-benzisothiazolin-3-one, 2' -dithio-bis (pyridine-1-oxide), and the like.

Examples of the ultraviolet absorber include commercially available ultraviolet absorbers such as: TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, TINUVIN326, etc., manufactured by BASF corporation.

Examples of the filler include: silica particles, diatomaceous earth, and the like. In addition, from the viewpoint of dispersibility, the filler is preferably particles having surfaces subjected to hydrophobic treatment. Examples of such a surface treatment method include a method of surface treatment using dimethylpolysiloxane, dimethyldichlorosilane, hexamethylenedisilazane, cyclic dimethylsiloxane, or the like. The average particle diameter of the particles having the surface subjected to the hydrophobic treatment is preferably 5nm to 300 nm.

Examples of the crosslinking agent include: isocyanate compounds, epoxy compounds, melamine compounds, metal chelate compounds,Oxazoline compounds, aziridine compounds, and the like.

The oil component is contained in the resin (matrix) composed of the polymer component, and the content ratio of the oil component is, for example, 25 to 400 parts by mass, preferably 50 to 300 parts by mass, more preferably 75 to 250 parts by mass, and particularly preferably 100 to 200 parts by mass, relative to 100 parts by mass of the polymer component. When the content of the oil component is 25 parts by mass or more per 100 parts by mass of the polymer component, the oil component can be sufficiently exuded, and the anti-icing effect can be exhibited. Further, by setting the content to 400 parts by mass or less, the strength of the oil-containing layer is not lowered.

In the present invention, the lower limit of the content of the polymer component in the entire oil-containing layer is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 25% by mass or more, and the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. When the content of the polymer component is within the above range, the oil component sufficiently bleeds out, and the anti-icing effect can be exhibited.

In order to contain an oil component in a resin composed of a polymer component, for example: a method of mixing a polymer component and an oil component, and if necessary, other components, and heating and curing the mixed resin composition. By heating the resin composition, the polymer component forms a matrix, and the oil component is dispersed therein.

The thickness of the oil-containing layer may be determined as appropriate depending on the purpose, and is preferably 0.05 to 3mm (50 to 3000 μm). When the layer thickness of the oil-containing layer is 0.05mm or more, the outdoor exposure durability is improved, and the amount of the oil component contained can be increased, so that the bleeding effect can be improved, and the snow and ice prevention function can be improved. Further, the workability is improved by setting the thickness of the oil-containing layer to 3mm or less. The lower limit of the layer thickness of the oil-containing layer is preferably 0.075mm or more, more preferably 0.1mm or more, and the upper limit is preferably 2.5mm or less, more preferably 2mm or less.

In the oil-containing layer, the oil component may be exuded at a predetermined temperature or lower, and the exudation temperature may be appropriately set depending on the use environment. For example, in the case where the predetermined temperature is set to 0 ℃, by appropriately selecting the oil component that bleeds out at 0 ℃ or lower, the oil component can be made to bleed out from the film when the outside air reaches 0 ℃ or lower.

< substrate >

In the membrane of the present invention, a substrate is preferably provided in order to support the oil-containing layer and maintain the strength of the membrane.

The material constituting the base material may be appropriately selected in consideration of the adhesiveness to the object, the strength of the entire product, and the like, and examples thereof include: polyurethane resins, polyurethane acrylic resins, rubber-based resins, vinyl chloride resins, polyester resins, silicone resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, and the like), ionomers, polyethylene terephthalate resins, and the like. Among them, polyester resins, ionomers, and polyethylene terephthalate resins are preferably used from the viewpoint of adhesiveness to an object. Such a base material layer may be one type only, or two or more types.

The thickness of the substrate may be determined as appropriate depending on the application, and is, for example, preferably 10 to 300. mu.m, more preferably 30 to 250. mu.m, and still more preferably 50 to 200. mu.m. By adjusting the layer thickness of the base material as described above, the film can have an appropriate strength and excellent handling properties.

< preparation of film >

The film of the present invention can be produced, for example, by a method of forming a coating film using a resin composition containing a polymer component and an oil component, and curing the coating film after providing unevenness to the surface of the coating film, a method of directly or indirectly providing another member having unevenness to a cured coating film formed using the resin composition, and a method of making the cured coating film follow the unevenness of the other member.

Specifically, the method for producing a film of the present invention includes the following steps (a) and (b), or includes the following step (c).

(a) A step of forming a coating film using a resin composition containing a polymer component and an oil component, and forming an uneven shape on the surface of the coating film

(b) Curing the coating film having the uneven shape formed thereon

(c) And forming a coating film using a resin composition containing a polymer component and an oil component, and curing the coating film, and then providing a member having irregularities on the surface thereof on one surface of the cured coating film to form irregularities on the surface of the coating film.

The film of the present invention is preferably produced by the above production method.

(Process (a))

In the step (a), first, a resin composition containing a polymer component and an oil component at an arbitrary ratio is prepared. The resin composition may contain other components as described above. The resin composition is preferably stirred until the raw material components become uniform, and a stirrer may be used.

In the case where air is contained in the resin composition, there is a possibility that air is contained in the oil-containing layer after molding, and in this case, there is a possibility that the film strength is lowered or the appearance of the product is deteriorated, so that it is preferable to perform deaeration. Examples of the method of degassing include: a method of defoaming in a range of several seconds to 5 minutes by a planetary stirring apparatus, and a method of vacuum treatment in a range of several seconds to 30 minutes under vacuum.

The resin composition obtained as described above is applied to a coating table or a substrate to form a coating film (oil-containing layer). The coating film may be applied so that the dried film thickness becomes 0.05 to 3mm, and the application method is not particularly limited, and examples thereof include a method of casting using a coater and a brush coating method.

Thereafter, a concave-convex shape is formed on the surface of the coating film. Examples of the method for forming the uneven shape in the coating film include: a method of transferring the irregularities to the coating film by closely adhering a roller having irregularities on the peripheral surface thereof to the coating film; a method of pressing a press sheet having irregularities on the surface thereof against a coating film to transfer the irregularities to the coating film; a method of pressing a sandpaper having irregularities on the surface thereof against a coating film to transfer the irregularities to the coating film. When the resin composition is coated with the brush, desired irregularities can be formed on the surface of the coating film at the same time as the coating, depending on the material of the brush.

The height of the irregularities can be appropriately adjusted by adjusting the pressing force of a processing member such as a roller or a press sheet to be provided with the irregularities.

(Process (b))

In the step (b), the coating film having the uneven shape formed thereon 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, a method of adding a crosslinking agent, and the like.

When the drying is performed by heating, the heating is preferably performed at 100 to 160 ℃ 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 at an arbitrary ratio. The method of forming the coating film can be performed in the same manner as in the step (a).

Thereafter, the coating film is cured to obtain a cured coating film. 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, a method of adding a crosslinking agent, and the like.

When the drying is performed by heating, the heating is preferably performed at 100 to 160 ℃ for 1 to 300 minutes.

After curing, a member having an uneven surface is provided on one surface of the cured coating film, specifically, on the substrate surface on the back surface of the coating film in the case where the cured coating film has a substrate, or on one main surface of 2 main surfaces in the case where the cured coating film is only a cured coating film. Examples of the member include: an adhesive layer having irregularities on the surface (e.g., a substrate-free adhesive sheet), a substrate having irregularities on the surface, and the like. As a result, the cured coating film follows the irregularities of the member having irregularities, and an irregular shape is formed on the surface of the coating film.

As described above, the film of the present invention can be obtained.

The thickness of the film of the present invention may be appropriately selected from the range of 0.06 to 3.5mm, in consideration of the desired strength of the film, the size of the object (structure) to which the film is applied, and the like.

In the present invention, the arithmetic average height (Sa) in a 3.2cm × 3.2cm region of the surface of the oil-containing layer of the film is 4 μm or more. When the arithmetic average height (Sa) is 4 μm or more, the desired effect of the present invention can be obtained. The lower limit of the arithmetic mean height (Sa) is preferably 4.3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more, and the upper limit is preferably 100 μm or less, more preferably 75 μm or less, and still more preferably 50 μm or less.

The arithmetic average height (Sa) can be obtained by imaging the surface of the film with a laser microscope (for example, "opterlics HYBRID" manufactured by Lasertec corporation) and calculating the average height in a region of 3.2cm × 3.2 cm.

In the present invention, the maximum pitch of the uneven shape is preferably 2000 μm or more. When the maximum pitch distance is 2000 μm or more, the film surface has a sufficient uneven shape, and thus has excellent skiing properties. The maximum pitch of the uneven shape is more preferably 2500 μm or more, and the upper limit is preferably 60000 μm or less, more preferably 55000 μm or less.

The film of the present invention can be used as a surface coating material to be provided on the surface of an object (structure). The object is not particularly limited as long as it is exposed to natural environments such as snowfall and wind and rain, and specifically, an airplane, a railway, an automobile, a wind turbine, a house, a signal light, a signboard, and the like can be used.

Examples

The present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

In the examples and comparative examples, "parts" appearing means a quality standard.

Production example 1 preparation of resin composition

50 parts of a silicone resin (both made by shin-Etsu chemical Co., Ltd., two-pack type RTV rubber) prepared by mixing KE-1950-50A and KE-1950-50B at a mass ratio of 1:1, 30 parts of KF-96-50cs (silicone oil made by shin-Etsu chemical Co., Ltd.), and 20 parts of TSF-437 (silicone oil made by Mitigo high and New Material Japan Co., Ltd.) were stirred and mixed until uniform to prepare a resin composition.

Production example 2 preparation of resin composition

50 parts of a silicone resin (two-component RTV rubber manufactured by shin-Etsu chemical Co., Ltd.) and 50 parts of ethyl acetate (Fuji film and Wako pure chemical industries, Ltd.) were mixed at a mass ratio of KE-1950-50A and KE-1950-50B of 1:1, and the mixture was stirred and mixed until uniform to prepare a resin composition.

(example 1)

The resin composition prepared in production example 1 was uniformly applied to a polyethylene terephthalate (PET) film (film thickness 125 μm) using an applicator so that the thickness of the dried oil-containing layer became 150 μm. The coating film was formed with irregularities by using a roll having irregularities on the periphery. Thereafter, the membrane of example 1 was prepared by drying at 150 ℃ for 10 minutes to form an oil-containing layer.

The surface of the film was photographed by a laser microscope ("opterlics HYBRID" manufactured by Lasertec corporation) and the average height was calculated by measuring the height in a 3.2cm × 3.2cm area, and the arithmetic average height (Sa) was 4.4 ± 1.0 μm.

(example 2)

A film of example 2 was produced in the same manner as in example 1, except that the unevenness was formed on the coating film by using a stamp. The arithmetic average height (Sa) of the film surface was 15.9. + -. 6.1. mu.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 arithmetic average height (Sa) of the film surface was 20.9. + -. 3.3. mu.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 arithmetic average height (Sa) of the film surface was 21.4. + -. 5.3. mu.m.

(example 5)

A film of example 5 was produced in the same manner as in example 2, except that a punched piece different from that of example 2 was used. The arithmetic average height (Sa) of the film surface was 24.9. + -. 5.0. mu.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 arithmetic average height (Sa) of the film surface was 26.1. + -. 5.2. mu.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 arithmetic average height (Sa) of the film surface was 30.3. + -. 6.1. mu.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 arithmetic average height (Sa) of the film surface was 46.2. + -. 10.2. mu.m.

(example 9)

The resin composition prepared in production example 1 was uniformly applied to a polyethylene terephthalate (PET) film (film thickness: 125 μm) using an applicator so that the thickness of the oil-containing layer after drying became 150 μm, and dried at 150 ℃ for 10 minutes to form an oil-containing layer. Then, an adhesive having an uneven shape with a minimum inter-undulation distance of 1500 μm and a maximum inter-undulation distance of 5000 μm was provided on the substrate surface of the film, and a film of example 9 was produced. The arithmetic average height (Sa) of the film surface was 8.7. + -. 2.8. mu.m.

Comparative example 1

The resin composition prepared in production example 1 was uniformly applied to a polyethylene terephthalate (PET) film (film thickness: 125 μm) using an applicator so that the thickness of the oil-containing layer after drying became 150 μm, and dried at 150 ℃ for 10 minutes to form an oil-containing layer, thereby preparing a film of comparative example 1. The arithmetic average height (Sa) of the film surface was 3.4. + -. 1.2. mu.m.

Comparative example 2

The film of comparative example 2 was produced by the same method as in comparative example 1, except that the resin composition produced in production example 2 was used. The arithmetic average height (Sa) of the film surface was 4.1. + -. 0.5. mu.m.

Comparative example 3

The resin composition prepared in production example 2 was uniformly applied to a polyethylene terephthalate (PET) film (film thickness 125 μm) using an applicator so that the thickness of the dried oil-containing layer became 150 μm. The roller having irregularities on the peripheral surface thereof was used to form irregularities on the coating film. Thereafter, the film of comparative example 3 was prepared by drying at 150 ℃ for 10 minutes to form an oil-containing layer. The arithmetic average height (Sa) of the film surface was 20.4. + -. 7.0. mu.m.

Comparative example 4

A film of comparative example 4 was produced in the same manner as in comparative example 3, except that a roll different from that of comparative example 3 was used. The arithmetic average height (Sa) of the film surface was 29.9. + -. 4.6. mu.m.

Comparative example 5

A film of comparative example 5 was produced in the same manner as in comparative example 3, except that a roll different from that of comparative example 3 was used. The arithmetic average height (Sa) of the film surface was 32.2. + -. 2.1. mu.m.

The films of the examples and comparative examples prepared above were subjected to the following skiing experiments.

The film produced in each example was cut into a length of 10cm by a width of 10cm (area of 100 cm)²) Is adhered to the oil-containing layer in a length of 10cm by 10cm (area of 100 cm) so that the oil-containing layer is a surface²) The acrylic plate of (2) was set in a laboratory having an ambient temperature of 1 ℃. About 20g of snow mass of wet snow was attached to the horizontally arranged film surface. The acrylic plate with the attached snow lump was set to be inclined by 60 ° with respect to the ground.

After that, the time until the snow lump fell (skiing time) was measured. The results are shown in Table 1.

Comparative example 1 is a film having an oil-containing layer on the film surface and no irregularities, and 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 have irregularities). It is understood that, although the skiing time is shorter in comparative example 1 than in comparative examples 2 to 5, the skiing time is significantly shorter in examples 1 to 9 than in comparative example 1, and the snow mass can be naturally dropped in a shorter time, thereby having an excellent anti-icing effect.

While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on the japanese patent application published on 27/3/2019 (japanese patent application 2019-061862), the contents of which are hereby incorporated by reference.

Industrial applicability

The film of the present invention is useful for preventing snow and ice from adhering to the surface of an airplane, a railway, an automobile, a wind power generator, a house, a signal lamp, a signboard, and the like.