WO2021060202A1 - 霜耐性を有する撥水膜及びその製造方法 - Google Patents

霜耐性を有する撥水膜及びその製造方法 Download PDF

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Publication number
WO2021060202A1
WO2021060202A1 PCT/JP2020/035555 JP2020035555W WO2021060202A1 WO 2021060202 A1 WO2021060202 A1 WO 2021060202A1 JP 2020035555 W JP2020035555 W JP 2020035555W WO 2021060202 A1 WO2021060202 A1 WO 2021060202A1
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Prior art keywords
water
repellent
layer
film
substrate
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PCT/JP2020/035555
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English (en)
French (fr)
Inventor
白鳥　世明
浩貴 中村
新太朗 大川
宏明 安藤
美貴 北元
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豊田合成株式会社
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Application filed by 豊田合成株式会社 filed Critical 豊田合成株式会社
Priority to EP20869880.3A priority Critical patent/EP4019242A4/en
Priority to CN202080066583.1A priority patent/CN114423605A/zh
Priority to US17/762,879 priority patent/US20220340799A1/en
Publication of WO2021060202A1 publication Critical patent/WO2021060202A1/ja

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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to a water-repellent film having frost resistance and a method for producing the same.
  • Japanese Patent No. 6333454 describes a water- and oil-repellent coating having a hydrophilic gel-type silica powder bonded to fluoroalkylsilane.
  • Japanese Unexamined Patent Publication No. 2009-073877 describes a solid polyhydric alcohol-based composition having an antifrost effect.
  • the water-repellent film has a problem of low resistance to frost. Therefore, one of the inventions described in this specification is an object of providing a water-repellent film having frost resistance and a method for producing the same. Another object of the invention described in this specification is to provide a film having both characteristics of preventing snow adhesion and preventing frost formation and a method for producing the same.
  • This invention is basically based on an example in which a water-repellent film having frost resistance can be obtained because it has a two-layer structure of a water-repellent porous layer and a hygroscopic layer.
  • the first invention disclosed in this specification relates to a water repellent film having frost resistance.
  • This film is a water-repellent film 1 having frost resistance, which includes a moisture-absorbing layer 5 provided on the substrate 3 and a water-repellent layer 7 provided on the moisture-absorbing layer 5.
  • the water-repellent layer 7 contains the water-repellent layer substrate 9 and the water-repellent component 11 adhering to the water-repellent layer substrate. Since the structure includes two layers, a moisture absorbing layer and a water repellent layer, a water repellent film having frost resistance could be obtained. Examples of water repellent components are particles, molecules, and oil layers.
  • the moisture absorbing layer 5 preferably contains an antifreeze liquid component. Hygroscopicity can be ensured even in a cold environment by containing an antifreeze component.
  • antifreeze components include one or more of polydimethylsiloxane, polyphenylmethylsiloxane, glycerin, ethylene glycol, polyethylene glycol, propylene glycol, polyvinyl alcohol, cellulose, acrylic acid-based antifreeze, and acrylamide-based antifreeze. ..
  • the moisture absorbing layer 5 preferably contains a first PEG having a weight average molecular weight of 100 or more and less than 800, and a second PEG having a weight average molecular weight of 800 or more and 20 million or less. Then, it is preferable that w 1 / w 2, which is the weight ratio of the first PEG and the second PEG, is 0.001 or more and 1000 or less.
  • water-repellent component 11 is water-repellent silica particles.
  • Another example of the water-repellent component 11 is a water-repellent compound attached to the water-repellent layer substrate.
  • the water-repellent compound is, for example, a compound having a functional group water-repellent group such as a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group at the end.
  • the example of the water-repellent layer substrate 9 is a porous one. Since the surface of the water-repellent layer substrate 9 is made porous, the snow on the surface of the water-repellent layer cannot penetrate into the inside and is removed. Further, since the surface of the water-repellent layer base 9 is made porous, water droplets on the surface of the water-repellent layer are absorbed by the moisture-absorbing layer, and the situation where the surface of the water-repellent layer base 9 freezes can be prevented.
  • An example of the surface of the substrate 3 has a polycarbonate, acrylic resin, or methacrylic resin.
  • This film has excellent affinity with polycarbonate, acrylic resin, or methacrylic resin, and is therefore preferably used in automobiles and aircraft.
  • Preferred uses for membranes are formed on the surface of parts related to the exterior and interior of automobiles, or on the surface of aircraft fuselage.
  • the spacer layer 13 existing between the moisture absorbing layer 5 and the water repellent layer 7 is further included. Since there is a spacer layer, the moisture absorbing layer can absorb the moisture adhering to the water repellent layer portion by allowing water vapor to pass through well. In addition, since there is a spacer layer, water vapor generated from the moisture absorbing layer can escape.
  • the spacer layer may be simply a frame or a pillar.
  • the following invention disclosed herein relates to a method for producing a water repellent film having frost resistance.
  • This method includes a hygroscopic layer forming step of forming a hygroscopic layer on the target surface and It includes a water-repellent layer forming step of forming a water-repellent layer on the moisture-absorbing layer.
  • the water-repellent layer forming step includes a step of adhering a water-repellent component to the water-repellent layer substrate.
  • One of the inventions described in this specification can provide a water repellent film having frost resistance and a method for producing the same.
  • One of the inventions described in this specification can provide a film having both characteristics of preventing snow adhesion and preventing frost formation and a method for producing the same.
  • FIG. 1 is a conceptual diagram showing a configuration example of a water-repellent film.
  • FIG. 2 is a photograph instead of a drawing showing a state when the removal performance of the supercooled water of Example 1 and Comparative Examples 1 and 2 was evaluated.
  • FIG. 3 is a photograph instead of a drawing showing a state when the snow adhesion prevention property of Examples 1, 2 and 3 was evaluated.
  • FIG. 1 is a conceptual diagram showing a configuration example of a water-repellent film.
  • the water-repellent film will be described below. As shown in FIG. 1, this film includes a moisture absorbing layer 5 provided on the substrate 3 and a water repellent layer 7 provided on the moisture absorbing layer 5.
  • Examples of the surface of the substrate 3 include polycarbonate, acrylic resin, or methacrylic resin.
  • This film has excellent affinity with polycarbonate, acrylic resin, or methacrylic resin, and is therefore preferably used in automobiles and aircraft.
  • Preferred uses for membranes are formed on the surface of parts related to the exterior and interior of automobiles, or on the surface of aircraft fuselage. Examples of parts related to the exterior of automobiles are doors, car bodies, windows, and frames. Examples of parts related to the interior of an automobile are cabinets, steering wheels, pedals, gears and the inner surface of the car body.
  • the substrate itself may be a resin or a metal.
  • the substrate when the substrate is a metal, it is preferable that the surface is coated with a resin layer containing polycarbonate, acrylic resin, or methacrylic resin.
  • the substrate may be a component including an aircraft frame or a component including an automobile frame. More preferably, by applying it to the surface of a millimeter wave or LiDAR transmission cover provided on the exterior of an automobile, the sensing accuracy can be improved regardless of the weather.
  • the hygroscopic layer 5 means a layer having hygroscopicity.
  • the hygroscopic layer is known, for example, as described in Japanese Patent No. 6396872.
  • Examples of the hygroscopic layer are a hygroscopic layer containing known hygroscopic agents such as silica gel, alumina gel, molecular sieve, zeolite, and calcium chloride and a resin as a dispersion medium, and a hygroscopic layer which is a microporous film carrying the hygroscopic agent. , Amorphous silica, a water-soluble resin, and a hygroscopic layer having a porous structure containing a hygroscopic agent.
  • the moisture absorbing layer 5 preferably contains an antifreeze liquid component. Hygroscopicity can be ensured even in a cold environment by containing an antifreeze component.
  • antifreeze components include one or more of polydimethylsiloxane, polyphenylmethylsiloxane, glycerin, ethylene glycol, polyethylene glycol, propylene glycol, polyvinyl alcohol, cellulose, acrylic acid-based antifreeze, and acrylamide-based antifreeze. .. Since these compounds and resins are known, known resins may be appropriately used. For example, Japanese Patent No.
  • 3299081 states that, on a weight basis, an antifreeze solution consisting of 250 to 300 parts of water and 5 to 10 parts of polyhydric alcohol, 10 to 50 parts of water-soluble acetate, and water-soluble rust preventive.
  • An antifreeze paint comprising 2.0 to 5.0 parts of an agent and 6 to 65 parts of a water-soluble binder is described.
  • the polyhydric alcohol is selected from ethyl glycol, butyl glycol, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, ethyldiglycol, butyldiglycol, glycerin, and propionylcarbinol1.
  • binders are biscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellol, soluble starch, carboxymethyl starch, dialdehyde starch, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, water soluble It is one or more resins selected from alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble acrylic resin, water-soluble epoxy resin, and water-soluble polybutadiene resin.
  • the antifreeze component in this specification a mixture of the polyhydric alcohol and the resin described in the above publication can be used as appropriate.
  • the moisture absorbing layer 5 preferably contains a first PEG having a weight average molecular weight of 100 or more and less than 800, and a second PEG having a weight average molecular weight of 800 or more and 20 million or less.
  • the weight average molecular weight of the first PEG may be 100 or more and less than 400, or 150 or more and less than 300.
  • the second PEG may contain a plurality of groups having different weight average molecular weights. Examples of the weight average molecular weight of the second PEG may be 850 or more and less than 2000, 900 or more and less than 2000, 950 or more and less than 1500, 2000 or more and less than 500,000, 2500 or more and less than 100,000, 2500 or more and less than 10,000.
  • w 1 / w 2 which is the weight ratio of the first PEG and the second PEG, is 0.001 or more and 1000 or less (preferably 0.01 or more and 500 or less, 0.01 or more and 100 or less, 0.1 or more). 10 or less, 0.01 or more and 1000 or less, 0.05 or more and 100 or less, 0.1 or more and 50 or less) are preferable.
  • the first PEG and the second PEG which are liquid and solid, respectively, in one of the assumed usage environments of the film (cold region), even if the film is formed in a tilted state, dripping or the like can occur. Hygroscopicity can be ensured without this.
  • the second PEG may not be required.
  • the moisture absorbing layer may have an appropriate thickness and concentration according to the application.
  • An example of the thickness of the moisture absorbing layer is 0.1 mm or more and 1 cm or less, 0.5 mm or more and 5 mm or less, or 0.5 mm or more and 2 mm or less.
  • the water-repellent layer 7 means a layer having a property of repelling water.
  • the water-repellent film and the water-repellent layer are known, for example, as described in Japanese Patent No. 6304411.
  • the angle between the water droplet and the sample surface when about 2 ⁇ L of pure water is placed on the surface of the water-repellent layer may be evaluated by measuring with a contact angle meter.
  • An example of a contact angle meter is a CA-X type manufactured by Kyowa Interface Science, which may be measured in the atmosphere (about 25 ° C.). In the initial contact angle, a contact angle of 80 ° or more is good, 108 ° or more is better, and 110 ° or more is even better.
  • the water-repellent film in this specification is a water-repellent film having frost resistance.
  • Frost resistance is a known performance, for example, as evaluated in Japanese Patent No. 656945.
  • the substrate may be cooled to ⁇ 15 ° C. in an environment of a temperature of 5 ° C. and a relative humidity of 50%, and the change over time of frost may be observed. Then, for example, a material having a superior frost change with time as compared with a glass substrate may be considered to have frost resistance.
  • the water-repellent layer 7 contains the water-repellent layer base 9 and the water-repellent component 11 adhering to the water-repellent layer base.
  • the example of the water-repellent layer substrate 9 is a porous one. Since the surface of the water-repellent layer substrate 9 is made porous, the snow on the surface of the water-repellent layer cannot penetrate into the inside and is removed. Further, since the surface of the water-repellent layer base 9 is made porous, water droplets on the surface of the water-repellent layer are absorbed by the moisture-absorbing layer, and the situation where the surface of the water-repellent layer base 9 freezes can be prevented.
  • the porous material may have holes at random positions or may be mesh-like.
  • an example of the porous mesh is 50 ⁇ m or more and 4000 ⁇ m or less, 100 ⁇ m or more and 2000 ⁇ m or less, 50 ⁇ m or more and 800 ⁇ m or less, or 100 ⁇ m or more and 600 ⁇ m or less. Good.
  • the thickness of the water-repellent layer substrate 9 is not particularly limited.
  • Examples of water repellent components are particles, molecules, and oil layers.
  • An example of water repellent particles is water repellent silica particles.
  • the water-repellent silica particles mean silica particles in which the surface of ordinary silica fine particles is chemically modified to impart water repellency.
  • Examples of modifying groups introduced into the surface of silica fine particles from the viewpoint of water repellency include methyl group, ethyl group, propyl group, butyl group, isopropyl group, fluorine atom, fluoromethyl group, difluoromethyl group and trifluoromethyl group. It is a hydrophobic group.
  • the water-repellent silica particles are described in, for example, JP-A-9-114414, JP-A-9-24016, JP-A-6-115924, and JP-A-2003-342017.
  • An example of the average particle size (D50) of the water-repellent silica particles is 10 nm or more and 500 nm or less, 30 nm or more and 400 nm or less, and 50 nm or more and 300 nm or less.
  • the average particle size (D50) is the particle size of the particles measured by dispersing the fine particles in water and using a particle size distribution measuring device using a laser diffraction method, and D50 is the particle size of 100 samples. It refers to the 50th particle size counted from the smallest particle size, and means the average particle size of the measurement sample.
  • the water-repellent silica particles may be attached to an appropriate concentration substrate.
  • the water-repellent component 11 is a water-repellent compound attached to the water-repellent layer substrate.
  • the water-repellent compound is, for example, a compound having a functional group water-repellent group such as a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group at the end.
  • a water-repellent component is an oil layer having water repellency. This can be formed by applying a water repellent resin to the substrate.
  • water-repellent resins are fluororesins and silicone resins.
  • Another example of the water-repellent resin is a resin whose surface is made water-repellent by mixing a fluorine-based additive with a resin such as a methacrylic resin, an acrylic resin, a urethane resin, or an epoxy resin.
  • a water-repellent layer can be obtained by applying an appropriate amount of a water-repellent resin to a substrate and solidifying it.
  • the spacer layer 13 existing between the moisture absorbing layer 5 and the water repellent layer 7 is further included. Since there is a spacer layer, the moisture absorbing layer can absorb the moisture adhering to the water repellent layer portion by allowing water vapor to pass through well. In addition, since there is a spacer layer, water vapor generated from the moisture absorbing layer can escape.
  • the thickness of the spacer may be appropriately adjusted from the above viewpoint. Examples of the thickness of the spacer layer are 10 ⁇ m or more and 2 mm or less, 40 ⁇ m or more and 1 mm or less, 50 ⁇ m or more and 1 mm or less, 100 ⁇ m or more and 1 ⁇ m or less, 50 ⁇ m or more and 500 ⁇ m or less, 100 ⁇ m or more. It may be 400 ⁇ m or less.
  • Examples of the porosity (opening ratio) of the spacer layer are 0.1% or more and 99.9% or less (or 1% or more and 99% or less, 3% or more and 10% or less, 3% or more and 50% or less, 5% or more. 20% or less, 5% or more and 15% or less).
  • the spacer layer may be simply a frame or a pillar.
  • the spacer layer may be in the form of a mesh.
  • a method for producing a water-repellent film having frost resistance includes a moisture-absorbing layer forming step of forming a moisture-absorbing layer on the target surface and a water-repellent layer forming step of forming a water-repellent layer on the moisture-absorbing layer.
  • the moisture-absorbing layer forming step is a step for forming a moisture-absorbing layer on the target surface.
  • the surface of the object constitutes the substrate.
  • a normally liquid resin and a normally solid resin heated and liquefied are mixed to prepare a coating liquid.
  • Various auxiliary materials may be added to the coating liquid. Therefore, the coating liquid is applied to the substrate by using an appropriate coating method according to the shape of the substrate. Examples of coating methods are spray coating, spin coating coating, roll coating coating and immersion coating.
  • Water-repellent layer forming step In the water-repellent layer forming step, a water-repellent component is attached to the water-repellent layer substrate to form a water-repellent layer. In the water-repellent layer forming step, a water-repellent layer is formed on the moisture-absorbing layer. At this time, a spacer may be installed on the moisture absorbing layer to form a water repellent layer on the spacer. For each layer, for example, a UV curable resin may be used to bond the moisture absorbing layer and the spacer layer, and the spacer layer and the water repellent layer. In addition, adjacent layers may be adhered using a known adhesive.
  • This film has water repellency, frost resistance, and snow removal performance. Therefore, for example, by forming a film on the surface of parts related to the exterior and interior of automobiles, the surface of aircraft parts, or the surface of buildings, these performances can be exhibited.
  • the contact angle and the fall angle may be evaluated.
  • supercooled water (-1 ° C, 10 ⁇ L) may be dropped from a height of 5 cm onto a substrate tilted at 20 ° and its behavior may be observed.
  • the substrate may be cooled to -15 ° C in an environment with a temperature of 5 ° C and a relative humidity of 50%, and the change over time of frost may be observed.
  • a substrate tilted at 70 ° is installed in an artificial snowmaking device (temperature: -15 ° C, snow depth: 4 cm / 1 hour (water equivalent 1 mm / 1 hour)), and changes over time are observed. do it.
  • a glass substrate manufactured by Matsunami Glass Co., Ltd.
  • a glass substrate manufactured by Matsunami Glass Co., Ltd.
  • Polyethylene glycol having a weight average molecular weight of 200 (manufactured by Wako Pure Chemical Industries, Ltd .: PEG200) is stirred with polyethylene glycol having a weight average molecular weight of 4 million (manufactured by Wako Pure Chemical Industries, Ltd .; PEG4M) heated to 150 ° C. Mixed while doing. In this way, a mixed solution was obtained. 2 g of the mixed solution was uniformly applied onto the glass substrate. As a result, a moisture absorbing layer having a thickness of about 1 mm was obtained on the substrate.
  • a polyester mesh (manufactured by Kubaa Co., Ltd.) with an opening of 174 ⁇ m and a thread system of 80 ⁇ m was prepared as a substrate.
  • Perfluoroalkyl group-containing silane (C6) manufactured by Gerest
  • silica manufactured by Aerosil Japan
  • ethanol ethanol
  • the liquid was prepared.
  • the silica fine particle dispersion was spray-coated on the substrate, and the silica fine particles were attached to the substrate. In this way, the water repellent layer was formed.
  • a PET film (manufactured by Toyobo Co., Ltd.) having a thickness of 180 ⁇ m was processed so as to have a shape similar to the outer frame of the substrate to form a frame body having a width of 3 mm.
  • Ultraviolet curable resin was applied to the upper surface and the lower surface of the frame.
  • a frame coated with an ultraviolet curable resin was mounted on a moisture absorbing layer.
  • a water-repellent layer is mounted on the upper part of the frame.
  • the substrate was irradiated with ultraviolet rays to cure the ultraviolet curable resin. In this way, a film was formed on the glass substrate.
  • Example 1 The physical characteristics of Example 1 and Comparative Examples 1 and 2 were evaluated. Table 1 shows the measurement results of the contact angle and the fall angle.
  • Comparative Examples 1 and 2 showed hydrophilicity, whereas Example 1 showed superhydrophobicity.
  • Example 1 the supercooled water removal performance of Example 1 and Comparative Examples 1 and 2 was observed.
  • the results are shown in FIG.
  • the first embodiment has the ability to remove supercooled water. It is considered that the reason for this is that an air layer is formed between the water-repellent layer and the moisture-absorbing layer by the spacer layer, and water droplets do not penetrate the water-repellent layer.
  • the spacer As the spacer, a processed PET film having a thickness of 180 ⁇ m was used. Although the spacer does not have to be present, it is preferable that the water-repellent layer and the moisture-absorbing layer can be separated from each other. Therefore, it is considered better to have a spacer. It is considered that the thickness of the spacer layer is preferably about 0.1 ⁇ m or more and about 1 cm, and it is considered that the thickness may be appropriately adjusted within this range. Further, although a PET film is used as the material, any material can be considered as long as it functions as a spacer.
  • Example 2 Examination of mesh diameter As the polyester mesh, a film having a mesh size of 352 ⁇ m and a thread system of 71 ⁇ m (Example 2) and a polyester mesh having a mesh size of 1293 ⁇ m and a thread system of 400 ⁇ m (Example 3) were used in the same manner as in Example 1. Was formed. The snow adhesion prevention property of Examples 1, 2 and 3 was evaluated. The result is shown in FIG. FIG. 3A shows the state of the film before snowfall, and FIG. 3B shows the state of the film 30 minutes after the start of snowfall. In FIG. 3, Comparative Examples 1 and Examples 1 to 3 are shown from the left. As shown in FIG.
  • Example 3 Examples 1 and 2 had a very high snow adhesion prevention property ( ⁇ ). On the other hand, in Example 3, the snow adhesion prevention property was higher than usual ( ⁇ ). It can be seen that the smaller the opening and the thread system, the higher the snow adhesion prevention property.
  • the present invention relates to a water-repellent film having frost resistance and a method for producing the same, it can be used in various industries in which damage occurs due to snow or frost. Examples of such industries are the aircraft industry, and the automobile industry.

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Abstract

基板３上に設けられた吸湿層５と，吸湿層５上に設けられた撥水層７とを含む，霜耐性を有する撥水膜１であって，撥水層７は，撥水層基体９と，撥水層基体に付着した撥水性成分１１を含む膜，及び霜耐性を有する撥水膜の製造方法であって，対象表面に吸湿層を形成する吸湿層形成工程と，吸湿層の上に撥水層を形成する撥水層形成工程とを含み，撥水層形成工程は，撥水層基体に，撥水性成分を付着させる工程を含む方法。

Description

霜耐性を有する撥水膜及びその製造方法
　この発明は，霜耐性を有する撥水膜及びその製造方法に関する。
　特許６３３３４５４号公報には，フルオロアルキルシランと結合した親水性ゲルタイプシリカ粉末を有する撥水・撥油性コーティングが記載されている。
　特開２００９－０７３８７７号公報には，防霜効果を有する固形状多価アルコール系組成物が記載されている。
特許６３３３４５４号公報 特開２００９－０７３８７７号公報
　撥水膜は，霜に対する耐性が低いという問題があった。
　そこで，この明細書に記載される発明のひとつは，霜耐性を有する撥水膜及びその製造方法を提供することを目的とする。
　また，この明細書に記載される発明のひとつは，雪の付着防止と霜の形成防止の両者の特性を併せ持つ膜及びその製造方法を提供することを目的とする。
　この発明は，基本的には，撥水性の多孔質層と，吸湿層の２層構造としたので，霜耐性を有する撥水膜を得ることができたという実施例に基づく。
　この明細書に開示される最初の発明は，霜耐性を有する撥水膜に関する。この膜は，基板３上に設けられた吸湿層５と，吸湿層５上に設けられた撥水層７とを含む，霜耐性を有する撥水膜１である。そして，撥水層７は，撥水層基体９と，撥水層基体に付着した撥水性成分１１を含む。吸湿層と撥水層との２層を含む構成としたので，霜耐性を有する撥水膜を得ることができた。撥水性成分の例は，粒子，分子，及び油層である。
　吸湿層５は，不凍液成分を含むものが好ましい。不凍液成分を含むことで寒冷環境においても吸湿性を担保できる。不凍液成分の例は，ポリジメチルシロキサン，ポリフェニルメチルシロキサン，グリセリン，エチレングリコール，ポリエチレングリコール，プロピレングリコール，ポリビニルアルコール，セルロース，アクリル酸系不凍液，及びアクリルアミド系不凍液の１種又は２種以上を含むものである。
　吸湿層５は，重量平均分子量が１００以上８００未満のポリエチレングリコールである第１のＰＥＧと，重量平均分子量が８００以上２０００万以下のポリエチレングリコールである第２のＰＥＧとを含むものが好ましい。そして，第１のＰＥＧと第２のＰＥＧの重量比であるｗ１／ｗ２が０．００１以上１０００以下であるものが好ましい。
　想定される膜の使用環境のひとつ（寒冷地）において，それぞれ液状及び固体である第１のＰＥＧ及び第２のＰＥＧを混合することで，膜を傾けた状態で形成しても液だれ等せずに吸湿性を担保できることとなる。なお，膜が平面に形成される場合は，第２のＰＥＧは不要となる。一方，例えば，自動車などに膜を形成する場合は，吸湿層が垂れないように第１のＰＥＧに第２のＰＥＧを混合することが好ましい。
　撥水性成分１１の例は，撥水性シリカ粒子である。撥水性成分１１の別の例は，撥水層基体に付着した撥水性化合物である。撥水性化合物は，例えば，端部に，フッ素原子，メチル基，フルオロメチル基，ジフルオロメチル基，トリフルオロメチル基などの官能基撥水性基を有する化合物である。
　撥水層基体９の例は，多孔質のものである。撥水層基体９の表面を多孔質としたので，撥水層の表面についた雪は内部に侵入できずに除去される。また，撥水層基体９の表面を多孔質としたので，撥水層の表面についた水滴は，吸湿層に吸収され，撥水層基体９の表面が凍結する事態を防止できる。
　基板３の表面の例は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂を有する。この膜は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂との親和性に優れるので，自動車や航空機に好ましく用いられる。膜の好ましい用途は，自動車外装および内装に関する部品表面，又は航空機の機体表面に形成される。
　吸湿層５と撥水層７の間に存在するスペーサ層１３をさらに含むものが好ましい。スペーサ層があるので，水蒸気などを良く通し，撥水層部分に付着した水分を吸湿層が吸湿できる。また，スペーサ層があるので，吸湿層から発生する水蒸気を逃がすことができる。　
　スペーサ層の空隙率の例は，０．１%以上９９．９％以下である。スペーサ層は，単なる枠や柱であってもよい。
　この明細書に開示される次の発明は，霜耐性を有する撥水膜の製造方法に関する。
　この方法は，対象表面に吸湿層を形成する吸湿層形成工程と，
　吸湿層の上に撥水層を形成する撥水層形成工程と，を含む。そして，撥水層形成工程は，撥水層基体に，撥水性成分を付着させる工程を含む。
この明細書に記載される発明のひとつは，霜耐性を有する撥水膜及びその製造方法を提供できる。
　この明細書に記載される発明のひとつは，雪の付着防止と霜の形成防止の両者の特性を併せ持つ膜及びその製造方法を提供できる。
図１は，撥水膜の構成例を示す概念図である。 図２は，実施例１及び比較例１，２の過冷却水の除去性能を評価した際の様子を示す図面に代わる写真である。 図３は，実施例１，２及び３の雪付着防止性を評価した際の様子を示す図面に代わる写真である。
　以下，図面を用いて本発明を実施するための形態について説明する。本発明は，以下に説明する形態に限定されるものではなく，以下の形態から当業者が自明な範囲で適宜修正したものも含む。
図１は，撥水膜の構成例を示す概念図である。以下，撥水膜について説明する。図１に示されるように，この膜は，基板３上に設けられた吸湿層５と，吸湿層５上に設けられた撥水層７とを含む。
　基板３の表面の例は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂を含むものである。この膜は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂との親和性に優れるので，自動車や航空機に好ましく用いられる。膜の好ましい用途は，自動車外装および内装に関する部品表面，又は航空機の機体表面に形成される。自動車の外装に関する部品の例は，ドア，車体，窓，及びフレームである。自動車の内装に関する部品の例は，キャビネット，ハンドル，べダル，ギア及び車体の内面部分である。基板自体が，樹脂であってもよいし，金属であってもよい。一方，基板が金属である場合は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂を含む樹脂層によりその表面が被覆されているものが好ましい。基板は，航空機の枠体を含む構成部品や自動車の枠体を含む構成部品であってもよい。より好ましくは，自動車外装に設けられる，ミリ波やＬｉＤＡＲの透過カバーの表面へ適用することで，天候によらずセンシング精度を高めることができる。
　吸湿層５は，吸湿性を有する層を意味する。吸湿層は，例えば特許６３９６８７２号公報に記載される通り公知である。吸湿層の例は，シリカゲル，アルミナゲル，モレキュラーシーブ，ゼオライト，及び塩化カルシウムなどの公知の吸湿剤と分散媒としての樹脂とを含む吸湿層，吸湿剤を担持した微多孔質膜である吸湿層，非晶質シリカ，水溶性樹脂，及び吸湿剤を含む多孔構造を有する吸湿層である。
　吸湿層５は，不凍液成分を含むものが好ましい。不凍液成分を含むことで寒冷環境においても吸湿性を担保できる。不凍液成分の例は，ポリジメチルシロキサン，ポリフェニルメチルシロキサン，グリセリン，エチレングリコール，ポリエチレングリコール，プロピレングリコール，ポリビニルアルコール，セルロース，アクリル酸系不凍液，及びアクリルアミド系不凍液の１種又は２種以上を含むものである。これらの化合物や樹脂は，公知であるから，公知の樹脂を適宜採用すればよい。例えば，特許第３２９９０８１号公報には，重量基準で，２５０～３００部の水及び５～１０部の多価アルコールからなる不凍液と，水溶性の酢酸塩１０～５０部と，水溶性の防錆剤２.０～５.０部と，水溶性のバインダ６～６５部とから成る凍結防止塗料が記載されている。そして，この文献において，多価アルコールは，エチルグリコール，ブチルグリコール，エチレングリコール，プロピレングリコール，ブチレングリコール，ポリエチレングリコール，ポリプロピレングリコール，エチルジグリコール，ブチルジグリコール，グリセリン，プロピオニルカルビノールから選択される１種又は２種以上とされ，バインダは，ビスコース，メチルセルロース，エチルセルロース，ヒドロキシエチルセルロース，カルボキシメチルセルロール，可溶性デンプン，カルボキシメチルデンプン，ジアルデヒドデンプン，ポリビニルアルコール，ポリアクリル酸ナトリウム，ポリエチレンオキシド，水溶性アルキド樹脂，水溶性メラミン樹脂，水溶性尿素樹脂，水溶性フェノール樹脂，水溶性アクリル樹脂，水溶性エポキシ樹脂，水溶性ポリブタジエン樹脂から選択される１種又は２種以上の樹脂とされている。この明細書における不凍液成分として，上記の公報に記載された多価アルコール及び樹脂を適宜混合したものを用いることができる。
　吸湿層５は，重量平均分子量が１００以上８００未満のポリエチレングリコールである第１のＰＥＧと，重量平均分子量が８００以上２０００万以下のポリエチレングリコールである第２のＰＥＧとを含むものが好ましい。
　第１のＰＥＧの重量平均分子量は，１００以上４００未満でもよいし，１５０以上３００未満でもよい。
　特に第２のＰＥＧは，重量平均分子量の異なる複数の群を含んでもよい。第２のＰＥＧの重量平均分子量の例は，８５０以上２０００未満，９００以上２０００未満，９５０以上１５００未満であってもよいし，２０００以上５０万未満，２５００以上１０万未満，２５００以上１万未満，３０００以上６０００未満であってもよいし，５０万以上２０００万以下，５０万以上１０００万以下，５０万以上８００万いか，１００万以上１０００万以下でもよい。
　そして，第１のＰＥＧと第２のＰＥＧの重量比であるｗ１／ｗ２が０．００１以上１０００以下（好ましくは，０．０１以上５００以下，０．０１以上１００以下，０．１以上１０以下，０．０１以上１０００以下，０．０５以上１００以下，０．１以上５０以下）であるものが好ましい。
　想定される膜の使用環境のひとつ（寒冷地）において，それぞれ液状及び固体である第１のＰＥＧ及び第２のＰＥＧを混合することで，膜を傾けた状態で形成しても液だれ等せずに吸湿性を担保できることとなる。なお，膜が平面に形成される場合は，第２のＰＥＧは不要であってもよい。一方，例えば，自動車の部品や飛行機の部品などに膜を形成する場合は，吸湿層が垂れないように第１のＰＥＧに第２のＰＥＧを混合することが好ましい。
　吸湿層は，用途に応じた適切な厚さや濃度とすればよい。吸湿層の厚さの例は０．１ｍｍ以上１ｃｍ以下であり，０．５ｍｍ以上５ｍｍ以下でもよいし，０．５ｍｍ以上２ｍｍ以下でもよい。
　撥水層７は，水をはじく性質を有する層を意味する。撥水膜や撥水層は，例えば，特許６３０４４１１号公報に記載される通り公知である。例えば，撥水層表面に，純水約２μＬを置いたときの水滴とサンプル表面とのなす角を接触角計で測定することで評価すればよい。接触角計の例は，協和界面科学製ＣＡ－Ｘ型であり，大気中（約２５℃）で測定すればよい。初期接触角において，接触角が８０°以上が良く，１０８°以上がよりよく，１１０°以上がさらに良い。
　この明細書における撥水膜は，霜耐性を有する撥水膜である。霜耐性については，例えば特許６５６６９４５号公報において評価される通り，公知の性能である。この明細書では，。耐霜性は，温度５℃，相対湿度５０％の環境下で基板を－１５℃に冷却し，霜の経時変化を観察すればよい。そして，例えば，ガラス基板に比べて霜の経時変化に優れるものを耐霜性があるものとすればよい。
　撥水層７は，撥水層基体９と，撥水層基体に付着した撥水性成分１１を含む。
　撥水層基体９の例は，多孔質のものである。撥水層基体９の表面を多孔質としたので，撥水層の表面についた雪は内部に侵入できずに除去される。また，撥水層基体９の表面を多孔質としたので，撥水層の表面についた水滴は，吸湿層に吸収され，撥水層基体９の表面が凍結する事態を防止できる。多孔質は，ランダムな位置に穴を有するものであってもよいし，メッシュ状のものであってもよい。多孔質がメッシュ状の場合，上記の観点から，多孔質の目開きの例は，５０μｍ以上４０００μｍ以下であり，１００μｍ以上２０００μｍ以下でもよいし，５０μｍ以上８００μｍ以下でもよいし，１００μｍ以上６００μｍ以下でもよい。撥水層基体９の厚さは特に限定されない。
撥水性成分の例は，粒子，分子，及び油層である。撥水性粒子の例は，撥水性シリカ粒子である。撥水性シリカ粒子は，通常のシリカ微粒子の表面を化学的に修飾し，撥水性を付与したシリカ粒子を意味する。撥水性の観点からシリカ微粒子表面に導入される修飾基の例は，メチル基，エチル基，プロピル基，ブチル基，イソプロピル基，フッ素原子，フルオロメチル基，ジフルオロメチル基，トリフルオロメチル基などの疎水性基である。撥水性シリカ粒子は，例えば特開平９－１１０４１４号公報，特開平９－２４１０１６号公報，特開平６－１１５９２４号公報，及び特開２００３－３４２０１７号公報に記載されている。
撥水性シリカ粒子の平均粒子径（Ｄ５０）の例は，１０ｎｍ以上５００ｎｍ以下であり，３０ｎｍ以上４００ｎｍ以下，５０ｎｍ以上３００ｎｍ以下でもよい。平均粒子径（Ｄ５０）とは，微粒子を水に分散させ，レーザー回折式による粒度分布測定装置を用いて測定した粒子の粒子径であり，Ｄ５０とは，１００サンプルの粒径を測定した時，粒径が小さいほうから数えて５０番目に当る粒径のことを指し，測定試料の平均の粒子径を意味する。撥水性シリカ粒子は，適切な濃度基体に付着させればよい。
撥水性成分１１の別の例は，撥水層基体に付着した撥水性化合物である。撥水性化合物は，例えば，端部に，フッ素原子，メチル基，フルオロメチル基，ジフルオロメチル基，トリフルオロメチル基などの官能基撥水性基を有する化合物である。
　撥水性成分の別の例は，撥水性を有する油層である。これは撥水性樹脂を基体に塗布することより形成できる。撥水性樹脂の例は，フッ素樹脂及びシリコーン樹脂である。撥水性樹脂の他の例は，メタクリル樹脂，アクリル樹脂，ウレタン樹脂，エポキシ樹脂などの樹脂に対してフッ素系添加剤を混合することで表面を撥水化した樹脂である。撥水性樹脂を適量基体に塗布し，固化させることで撥水層を得ることができる。
　吸湿層５と撥水層７の間に存在するスペーサ層１３をさらに含むものが好ましい。スペーサ層があるので，水蒸気などを良く通し，撥水層部分に付着した水分を吸湿層が吸湿できる。また，スペーサ層があるので，吸湿層から発生する水蒸気を逃がすことができる。スペーサの厚さは，上記の観点から適宜調整すればよい。スペーサ層の厚さの例は，１０μｍ以上２ｍｍ以下であり，４０μｍ以上１ｍｍ以下でもよいし，５０μｍ以上１ｍｍ以下でもよいし，１００μｍ以上１μｍ以下でもよいし，５０μｍ以上５００μｍ以下でもよいし，１００μｍ以上４００μｍ以下でもよい。
　スペーサ層の空隙率（開孔率）の例は，０．１%以上９９．９％以下（又は１％以上９９％以下，３％以上１０％以下，３％以上５０％以下，５％以上２０％以下，５％以上１５％以下）である。スペーサ層は，単なる枠や柱であってもよい。スペーサ層は，メッシュ状でもよい。
　次に，霜耐性を有する撥水膜の製造方法について説明する。対象表面に吸湿層を形成する吸湿層形成工程と，吸湿層の上に撥水層を形成する撥水層形成工程と，を含む。
　吸湿層形成工程
　吸湿層形成工程は，対象表面に吸湿層を形成するための工程である。対象物の表面が，基板を構成する。吸湿層形成工程では，通常液体の樹脂と，通常固体の樹脂を加熱して液化したものとを混合し，塗布液を調整する。塗布液には，各種副素材を添加してもよい。として，基板の形状などに応じて適切な塗布方法を用いて，塗布液を基板に塗布する。塗布方法の例は，スプレー塗布，スピンコート塗布，ロールコート塗布及び浸漬塗布である。
　撥水層形成工程
撥水層形成工程は，撥水層基体に，撥水性成分を付着させ撥水層を形成する。撥水層形成工程では，吸湿層の上に撥水層を形成する。この際に，吸湿層にスペーサを設置し，スペーサ上に撥水層を形成してもよい。各層は，例えばＵＶ硬化性樹脂を用いて，吸湿層とスペーサ層，スペーサ層と撥水層とを接着してもよい。また，公知の接着剤を用いて，隣接する層を接着してもよい。
この膜は，撥水性や耐霜性，除雪性能を有する。このため，例えば自動車外装および内装に関する部品表面や航空機部品の表面又は建築物の表面に膜を形成することで，これらの性能を発揮させることができる。
　撥水性の評価
撥水性は，接触角，転落角を評価すればよい。
　耐過冷却水に対する試験
　耐過冷却水については，２０°に傾けた基板に高さ５ｃｍから過冷却水（－１℃，１０μＬ）を滴下し，その挙動を観察すればよい。
　耐霜性の評価
　耐霜性は，温度５℃，相対湿度５０％の環境下で基板を－１５℃に冷却し，霜の経時変化を観察すればよい。
　雪の付着防止能の評価
人工降雪装置内（温度：－１５℃，積雪深：４ｃｍ／１時間（水換算１ｍｍ／１時間））に，７０°に傾けた基板を設置し，経時変化を観察すればよい。
　基板として，２．５ｃｍ×７．６ｃｍの大きさのガラス基板（松波硝子社製）を用いた。重量平均分子量２００のポリエチレングリコール（和光純薬社製：ＰＥＧ２００）に対し，１５０℃に加熱した重量平均分子量４００万のポリエチレングリコール（和光純薬社製；ＰＥＧ４Ｍ）を１０：１の重量比で攪拌しつつ混合した。このようにして混合液を得た。混合液２ｇをガラス基板上に均一に塗布した。その結果，基板上に厚さ約１ｍｍの吸湿層が得られた。目開き１７４μｍ，糸系８０μｍのポリエステルメッシュ（くればぁ社製）を基体として準備した。パーフルオロアルキル基含有シラン（Ｃ６）（ゲレスト社製），シリカ（日本アエロジル社製）及びエタノールを１重量％，１．５重量％及び９７．５重量％の重量比で混合し，シリカ微粒子分散液を準備した。シリカ微粒子分散液を基体にスプレー塗布し，シリカ微粒子を基体に付着させた。このようにして撥水層を形成した。
　厚さが１８０μｍであるＰＥＴフィルム（東洋紡社製）を基板の外枠と同様な形状となるように加工し，幅３ｍｍの枠体を形成した。枠体の上面及び下面に紫外線硬化性樹脂を塗布した。紫外線硬化性樹脂を塗布した枠体を吸湿層上に搭載した。枠体の上部に撥水層を搭載した。その後，基板に紫外線を照射し，紫外線硬化性樹脂を硬化させた。
　このようにしてガラス基板上に，膜を形成した。
　［比較例］
　ガラス基板そのものを比較例１とした。
　撥水層を設けなかった以外は，実施例１と同様にして膜を形成した（比較例２）
　実施例１及び比較例１，２の物性を評価した。
接触角及び転落角の測定結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように，比較例１,２は親水性を示すことに対し，実施例１は超撥水性を示した。
　次に，実施例１及び比較例１，２の過冷却水の除去性能を観測した。その結果を，図２に示す。図２に示されるように，実施例１は過冷却水の除去性能を有する。この理由は，スペーサ層によって撥水層と吸湿層の間に空気層が形成され，水滴が撥水層を貫通しないためであると考えれる。
　スペーサとして，厚さ１８０μｍであるＰＥＴフィルムを加工したものを用いた。スペーサは，存在しなくてもよいものの，撥水層と吸湿層とを離すことができることが好ましい。このため，スペーサが存在した方が良いと考えられる。スペーサ層の厚さは，０．１μｍ以上１ｃｍ程度が好ましいと考えられ，この範囲で適宜調整してもよいと考えらえる。また，素材としてＰＥＴフィルムを用いたものの，スペーサとして機能するものであれば，材質を問わないと考えられる。
　［実施例２，３］
　メッシュ径の検討
　ポリエステルメッシュとして，目開き３５２μｍ及び糸系７１μｍのもの（実施例２），目開き１２９３μｍ及び糸系４００μｍのもの（実施例３）を用いた以外は実施例１と同様にして膜を形成した。実施例１，２及び３の雪付着防止性を評価した。その結果を図３に示す。
　図３（ａ）は，降雪前の膜の様子を示し，図３（ｂ）は降雪開始から３０分後の膜の様子を示す。図３において，左から比較例１，実施例１～３を示す。図３に示される通り，，実施例１及び２は，雪付着防止性が非常に高かった（◎）。一方，実施例３は，雪付着防止性が通常より高い程度（△）であった。目開き及び糸系が小さいほど高い雪付着防止性を示すことがわかる。
　［実施例４～１３］
　吸湿層を構成する樹脂の検討
　吸湿層を得るための樹脂成分を表２に示す組成とした以外は，比較例２と同様にして膜を形成した。得られた膜の防霜性能を併せて表２に示す。
Figure JPOXMLDOC01-appb-T000002
　このことから，ＰＥＧ２００の割合が多いほど ，高い防霜性能を示すことが分かる。
このことは，ＰＥＧの分子量が低くなる程，吸湿性が向上する事に起因する。
　この発明は霜耐性を有する撥水膜及びその製造方法に関するので，雪や霜で障害が発生する各種産業において利用され得る。そのような産業の例は，航空機産業，及び自動車産業である。
１　撥水膜
３　基板
５　吸湿層
７　撥水層
９　撥水層基体
１１　撥水性成分
１３　スペーサ層

Claims (12)

  1. 　基板（３）上に設けられた吸湿層（５）と，前記吸湿層（５）上に設けられた撥水層（７）とを含む，霜耐性を有する撥水膜（１）であって，
    　前記撥水層（７）は，撥水層基体（９）と，前記撥水層基体に付着した撥水性成分（１１）を含む，
    　膜。
  2. 　請求項１に記載の膜であって，
    　前記吸湿層（５）は，不凍液成分を含む膜。
  3. 　請求項２に記載の膜であって，
    　前記不凍液成分は，ポリジメチルシロキサン，ポリフェニルメチルシロキサン，グリセリン，エチレングリコール，ポリエチレングリコール，プロピレングリコール，ポリビニルアルコール，セルロース，アクリル酸系不凍液，及びアクリルアミド系不凍液の１種又は２種以上を含む，膜。
  4. 　請求項１に記載の膜であって，
    　前記吸湿層（５）は，
    　重量平均分子量が１００以上８００未満のポリエチレングリコールである第１のＰＥＧと，
    　重量平均分子量が８００以上２０００万以下のポリエチレングリコールである第２のＰＥＧとを含み，
    　第１のＰＥＧと第２のＰＥＧの重量比であるｗ１／ｗ２が０．００１以上１０００以下である，膜。
  5. 　請求項１に記載の膜であって，
    　前記撥水性成分（１１）は，撥水性シリカ粒子である，膜。
  6. 　請求項１に記載の膜であって，
    　前記撥水性成分（１１）は，前記撥水層基体に付着した撥水性化合物である，膜。
  7. 　請求項１に記載の膜であって，
    　前記撥水層基体（９）は多孔質である，膜。
  8. 　請求項１に記載の膜であって，
    　前記基板（３）の表面は，ポリカーボネート，アクリル樹脂，又はメタクリル樹脂を有する膜。
  9. 　請求項７に記載の膜であって，
    　前記吸湿層（５）と前記撥水層（７）の間に存在するスペーサ層（１３）をさらに含む，膜。
  10. 　請求項９に記載の膜であって，
    　前記スペーサ層の空隙率が０．１%以上９９．９％以下である，膜。
  11. 　請求項１～１０のいずれかに記載の膜であって，
    　自動車外装および内装に関する部品表面，又は航空機の機体表面に形成される，膜。
  12. 　霜耐性を有する撥水膜の製造方法であって，
    　対象表面に吸湿層を形成する吸湿層形成工程と，
    　前記吸湿層の上に撥水層を形成する撥水層形成工程とを含み，
    　前記撥水層形成工程は，
    　　撥水層基体に，撥水性成分を付着させる工程を含む，
    方法。
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