Anti-icing material

Abstract

To provide an anti-icing material that prevents ice from adhering to the surface or can easily remove the ice once adhering thereto.SOLUTION: An anti-icing material includes a) a substrate and b) a functional layer formed on the substrate surface. (1) The functional layer includes (1a) a primer layer that includes an organic binder, and a filler including a core part and needle-like parts extending in at least two different directions from the core part, and also has an uneven surface formed by the needle-like parts of the filler, and (1b) a surface layer formed on the uneven surface. (2) The surface layer is composed of a liquid membrane of hydrophobic liquid.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel anti-icing material. In particular, the present invention relates to an anti-icing material having a surface on which ice is unlikely to adhere or from which adhered ice can be easily removed. [Background technology]

[0002] In snowy regions, snow accumulates on roofs, tunnel entrances, culverts, etc., and gradually grows into large snow masses. If these masses are left unattended, various problems can occur.

[0003] For example, when snow masses that have formed on roofs melt on the underside due to radiant heat from the sun or conductive heat from inside the building when the weather improves, they cause an avalanche on the sloping roof, which then falls from the eaves, damaging objects below or hitting passersby. Even if the snow mass does not fall, meltwater moves along the slope of the underside of the snow mass, and freezes when exposed to the outside air at its edge, forming dangerous icicles or cornices that hang down from the eaves and push against and destroy the wall directly below. In addition, meltwater that does not freeze can run down the eaves and cause leaks (melted water seeping into the room through gaps in the roofing materials).

[0004] In order to solve such problems, many techniques have been proposed, such as techniques to prevent falling snow blocks and the formation of icicles and snow cornices, as well as techniques to prevent ice leakage and snow entrapment. These techniques include various physical and chemical methods, and in particular, a method of preventing icing by coating the material surface with a composition that modifies the surface is also known.

[0005] In this case, particularly when the adhesion force of ice or snow blocks to structures, etc. (ice adhesion force) becomes large, the ice blocks do not easily detach, and when the ice blocks, etc. become large and heavy, they may fall. If such a phenomenon occurs, there is a risk of causing various accidents. Therefore, recently, technologies have been proposed that reduce the ice adhesion force so that ice or snow blocks attached to structures, etc. can easily detach (fall, be removed, etc.) from the structures before they become too large.

[0006] For example, a snow and ice accretion prevention agent is known, which comprises a liquid composition containing at least one selected from the group consisting of polysiloxane compounds having a hydrolyzable functional group or a condensable functional group and hydrolysis products of the polysiloxane compounds having the hydrolyzable functional group (Patent Document 1).

[0007] However, such conventional techniques are still not sufficient in reducing the adhesion force of ice, and there is still room for improvement in this regard.

[0008] In this regard, it has been reported that in order for ice blocks that have grown and frozen due to natural wind and rain to fall naturally, the ice adhesion strength must be 20 kPa or less (Non-Patent Document 1). However, when the inventors of the present application actually conducted an experiment in which they prototyped a member based on the technology in the above-mentioned document and allowed it to freeze, it was confirmed that it exhibited a high ice adhesion strength of 150 to 350 kPa. In other words, it can be said that a considerable force is required to remove ice that has adhered to an object without using thermal energy or the like. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication WO2020 / 31300 [Non-patent literature]

[0010] [Non-Patent Document 1] Kreder Michael,Nat.Rev.Matter.,2016,1,15003 Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, a main object of the present invention is to provide an anti-icing material that is less likely to have ice adhere to its surface or from which adhered ice can be easily removed. In particular, an object of the present invention is to provide an anti-icing material that can achieve a lower ice adhesion force. [Means for solving the problem]

[0012] Means of the Invention The present inventors have conducted intensive research in light of the problems in the prior art and have found that a material having a specific composition and structure can achieve the above object, thereby completing the present invention.

[0013] That is, the present invention relates to the following anti-icing material. 1. A material comprising: a) a substrate; and b) a functional layer formed on a surface of the substrate, (1) The functional layer comprises: (1a) a base layer including an organic binder and a filler having a core and needle-like portions extending from the core in at least two or more different directions, the base layer having an uneven surface formed by the needle-like portions of the filler; and (1b) a surface layer formed on the uneven surface; (2) The surface layer is composed of a liquid film of a hydrophobic liquid agent. An anti-icing material characterized by the above. 2. The anti-icing material according to item 1, wherein the undercoat layer has a porous structure and the hydrophobic liquid agent is contained in the voids of the porous structure. 3. The anti-icing material according to item 1, wherein the filler is an inorganic particle having needle-shaped portions extending from a core portion in four different axial directions. 4. The anti-icing material according to item 1, wherein the hydrophobic liquid contains at least one of silicone oil and fluorine oil. 5. The anti-icing material according to item 1, wherein the functional layer contains 8 to 60% by weight of the filler and 10 to 80% by weight of the hydrophobic liquid agent, with the entire functional layer being taken as 100% by weight. 6. The ice-proof material according to item 1, wherein the organic binder contains at least one of a resin, a rubber, and an elastomer. 7. A method for producing an anti-icing material comprising: a) a substrate; and b) a functional layer formed on a surface of the substrate, the method comprising the steps of: (1) preparing a coating material including an organic binder and a filler having a core and needle-shaped portions extending in at least two or more different directions from the core; (2) applying the coating material to a substrate and drying the coating material to form a base layer; and (3) forming a functional layer by applying a hydrophobic liquid agent to the surface of the underlayer; A method for producing an anti-icing material, comprising: Effect of the Invention

[0014] According to the present invention, it is possible to provide an anti-icing material on whose surface ice is unlikely to adhere or from which adhered ice can be easily removed. In particular, it is possible to provide an anti-icing material capable of realizing a lower ice adhesion force. In particular, in the present invention, a liquid film of a hydrophobic liquid agent is formed on the surface of a base layer containing a substance having a specific particle shape, so that a low ice adhesion force can be realized. For example, as shown in the examples described later, it is possible to achieve a low ice adhesion force of 20 kPa or less (particularly 19 kPa or less, further 4 to 18 kPa). As a result, even if ice or snow blocks are formed on the material of the present invention, they can be detached from the material of the present invention at a stage when their own weight is relatively light (for example, before reaching a dangerous weight). [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram showing an example of a layer structure of an anti-icing material of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] 1. Anti-icing material The anti-icing material of the present invention (the material of the present invention) is a material comprising: a) a substrate; and b) a functional layer formed on a surface of the substrate, (1) The functional layer comprises: (1a) a base layer including an organic binder and a filler having a core and needle-like portions extending from the core in at least two or more different directions, the base layer having an uneven surface formed by the needle-like portions of the filler; and (1b) a surface layer formed on the uneven surface; (2) The surface layer is composed of a liquid film of a hydrophobic liquid agent. It is characterized by:

[0017] An example of the layer structure of the material of the present invention is shown in Figure 1. The basic structure of the anti-icing material 10 in Figure 1 is, from the bottom up, a substrate 11 and a functional layer 12. The functional layer 12 has, from the bottom up, a base layer 12a and a surface layer 12b. That is, the surface layer 12b is formed on the surface of the base layer 12a opposite to the surface in contact with the substrate 11. Usually, the surface layer 12b is formed as the outermost layer of the material of the present invention.

[0018] In FIG. 1, the substrate 11 is in the form of a plate or a film, but is not limited thereto, and substrates having various shapes (three-dimensional shapes) can also be used.

[0019] Here, the underlayer 12a has a composition including an organic binder and a filler having a core and needle-like parts extending from the core in at least two or more different directions (hereinafter also referred to as the "filler of the present invention"). Therefore, in the underlayer 12a, the filler of the present invention is dispersed and fixed in the base material including the organic binder.

[0020] Each particle constituting the packing material of the present invention has a shape having a core and needle-like parts extending from the core in at least two or more different directions. Preferably, the packing material of the present invention is a particle (particle group) having a roughly tetrapod-like shape with four legs. The needle-like parts of the particles (particularly the parts corresponding to the four legs of the tetrapod-like particles) protrude from the surface of the base layer to form a plurality of protrusions p, which form a certain degree of unevenness on the surface of the base layer opposite the substrate 11.

[0021] The surface layer 12b is formed on the uneven surface of the base layer 12a thus formed. The surface layer 12b is composed of a liquid film of a hydrophobic liquid agent (e.g., an oil film, etc.). Therefore, the surface of the surface layer 12b (i.e., the surface exposed to the outside air) also has an uneven surface. And this liquid film is disposed on the outermost surface of the material of the present invention.

[0022] (1) Base material The substrate mainly serves as the base (support member) of the material of the present invention, i.e., has the function of imparting strength, stiffness, etc. to the anti-icing material.

[0023] The type of the substrate is not particularly limited, and metals (including alloys), resins, rubbers, fibrous materials, glasses, ceramics, etc., or composite materials thereof can be used. The shape of the substrate is also not limited, and may be, for example, a sheet, film, plate, or foil (hereinafter, these are also collectively referred to as "sheet"), as well as any of various three-dimensional shapes such as a sphere or a rectangular parallelepiped.

[0024] In particular, when the substrate has a sheet shape (e.g., a thickness of about 5 μm to 20 mm), at least one material such as a metal plate, metal foil, resin plate, resin sheet, nonwoven fabric, rubber sheet, rubber plate, wood piece, synthetic paper, glass plate, ceramic plate, resin coating, metal coating, etc. can be suitably used.

[0025] The type of the metal plate is not particularly limited, and at least one of aluminum plate, iron plate, copper plate, stainless steel plate, etc., having a thickness of 1 mm to 10 mm, can be preferably used. The type of the metal foil is also not particularly limited, and at least one of aluminum foil, iron foil, copper foil, stainless steel foil, etc., having a thickness of 10 μm to 500 μm can be preferably used.

[0026] The type of the resin plate or resin sheet is not particularly limited, and at least one type of polyester resin (e.g., polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin) having a thickness of 25 μm or more and 2 mm or less, polyolefin resin (e.g., polyethylene resin, polypropylene resin), etc. can be suitably used.

[0027] Among these, resins (particularly synthetic resins) are preferred from the viewpoints of the strength of the anti-icing material, ease of installation, etc. Therefore, for example, resin plates, resin sheets, resin films, etc. can be more suitably used as the substrate.

[0028] (2) Functional layer The functional layer is formed on the surface of the substrate, and exhibits an anti-icing function through the synergistic action of the base layer and the surface layer.

[0029] The functional layer has (1a) a base layer including an organic binder and a filler having a core and needle-shaped portions extending from the core in at least two or more different directions, and having an uneven surface formed by the needle-shaped portions of the filler, and (1b) a surface layer formed on the uneven surface.

[0030] base layer The underlayer is composed of a composition including an organic binder, a core, and a filler having a needle-shaped portion extending from the core in at least two or more different directions. The underlayer has a function of, in particular, retaining a hydrophobic liquid agent and exerting a desired anti-icing performance. If a low-viscosity hydrophobic liquid agent is applied to a substrate without a underlayer, the hydrophobic liquid agent will run down from the substrate, and a desired coating amount cannot be obtained. In addition, even if a high-viscosity hydrophobic liquid agent is used, if there is no underlayer, the hydrophobic liquid agent will not be retained, and unevenness will occur on the surface, which may prevent the anti-icing performance from being fully exerted.

[0031] In the present invention, the organic binder has a function of bonding the particles constituting the filler together or bonding the filler and the base material. The organic binder is not particularly limited, and preferably contains at least one of resin, elastomer, and rubber. The solid content in these organic binders can be, for example, within the range of about 90 to 100% by weight, but is not limited thereto.

[0032] As the resin, known or commercially available synthetic resins can be suitably used. For example, polyolefin resins (e.g., polyethylene resin, polypropylene resin, etc.), polyurethane resin, acrylic resin, polystyrene resin, ABS resin, vinyl chloride resin, polyamide resin, polycarbonate resin, polyacetal resin, fluorine resin, polyester resin (e.g., polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, etc.), silicone resin, etc., as well as blended resins thereof, copolymers containing a combination of two or more monomers constituting these resins, modified resins thereof, etc. can be used. These can be used alone or in combination of two or more.

[0033] In addition, known or commercially available elastomers and rubbers can be used. For example, polystyrene-based elastomers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products of these block copolymers; polyurethane-based elastomers consisting of diisocyanates and short-chain diols (so-called chain extenders), and long-chain polyols such as polyester polyols, polyether polyols, and polycarbonate polyols and diisocyanates; olefin-based elastomers such as polyisobutylene, butyl rubber (isobutylene-isoprene copolymers and modified products of said polymers), and polybutene; and synthetic rubbers such as polychloroprene rubber and nitrile rubber. These can be used alone or in combination of two or more.

[0034] The content of the organic binder in the underlayer is not limited, but is usually about 5 to 90% by weight, preferably 10 to 80% by weight, and most preferably 30 to 75% by weight.

[0035] The filler of the present invention uses particles (particle group) having a core and needle-like portions extending from the core in at least two or more different directions. In the present invention, it is particularly preferable that the particles have a three-dimensional shape having a core and needle-like portions extending from the core in four different axial directions. In particular, when imagining a regular tetrahedron with the core as the center of gravity, it is more preferable that each needle-like portion has a shape extending in the direction of the four vertices of the regular tetrahedron with the core as the center of gravity. As a specific example, it is preferable that the particles have a three-dimensional shape generally called a "tetrapod shape" (a three-dimensional shape having a core and needle-like portions extending from the core in four different axial directions).

[0036] The shape of the needle-like portion is not particularly limited as long as it is needle-like or a shape similar thereto (rod-like, cone-like, etc.), but preferably has an aspect ratio of 3 or more. The length of each needle-like portion is not particularly limited, but preferably is approximately the same. The length of the needle-like portion is not particularly limited, but is preferably usually about 1 to 50 μm as an average length, and more preferably 5 to 30 μm.

[0037] The material of the filler of the present invention is not particularly limited, and known inorganic materials can be suitably used. Examples of inorganic materials include metal oxides such as alumina, potassium titanate, wollastonite, zinc oxide, and aluminum borate, metal elements such as chromium, copper, iron, and nickel, or alloys thereof, inorganic materials other than metals such as silicon carbide, graphite, and silicon nitride, as well as composites thereof. Among these, metal oxides are preferred in that the effects of the present invention can be more reliably obtained, and it is more preferable that each of the needle-shaped parts is a particle composed of a single crystal of a metal oxide.

[0038] The content of the filler of the present invention in the undercoat layer is not particularly limited, but is usually about 5 to 95% by weight, particularly preferably 20 to 90% by weight, and most preferably 25 to 70% by weight. If the filler of the present invention is too small, the hydrophobic liquid may not sufficiently penetrate the unevenness of the functional layer surface, and the anti-icing properties may be reduced. If the filler of the present invention is too large, the viscosity of the mixture may be high, and the functional layer may not be uniformly laminated on the substrate surface, and unevenness may not be formed on the functional layer surface.

[0039] In addition, other additives may be contained in the undercoat layer within a range that does not impair the effects of the present invention. For example, fillers other than the filler of the present invention, pigments, antisettling agents, defoamers, hardening accelerators, ultraviolet absorbers, antioxidants, surface conditioners, viscosity adjusters, leveling agents, dispersants, plasticizers, and preservatives can be mentioned, and any of them can be used as publicly known or commercially available ones. When these are blended, the amount of addition can be, for example, about 5% by weight or less in total, but is not limited thereto.

[0040] In the present invention, the undercoat layer has an uneven surface formed by the needle-like portion of the filler. That is, the surface of the undercoat layer (the surface on which the surface layer is laminated) has a predetermined uneven surface. This can provide the effect of imparting water repellency and retaining the functional layer. The degree of unevenness is not limited, but it is usually preferable that the surface roughness is about 2 to 50 μm, and more preferably about 5 to 30 μm. The surface roughness in the present invention is the arithmetic mean roughness value measured with "Surfcom 1400D" manufactured by Tokyo Seimitsu Co., Ltd.

[0041] Furthermore, in the material of the present invention, it is preferable that the underlayer has a porous structure. In particular, the fillers of the present invention are intertwined with each other to effectively form voids, thereby creating a porous three-dimensional network structure. As a result, the hydrophobic liquid agent can be retained in the voids of the porous structure, and even if the liquid film on the surface of the unevenness is peeled off, the hydrophobic liquid agent present in the voids in the porous structure is expected to seep out to the surface of the unevenness due to capillary action or the like, thereby exhibiting a self-repairing effect. Therefore, in the present invention, it is preferable that at least a part of the hydrophobic liquid agent is impregnated into the voids of the porous structure constituting the underlayer.

[0042] When the base layer has a porous structure, its porosity is not particularly limited, but is usually preferably within the range of about 10 to 70%. By having the porosity within the above range, a higher anti-icing effect can be obtained. The porosity of the base layer can be measured, for example, by specific surface area measurement, cross-sectional observation, and image analysis from cross-sectional observation.

[0043] surface The surface layer of the material of the present invention is made of a liquid film of a hydrophobic liquid agent, which, together with the uneven surface, provides excellent anti-icing properties.

[0044] The hydrophobic liquid agent is not particularly limited as long as it is liquid under normal temperature and pressure, but it is preferable that the hydrophobic liquid agent contains at least one of fluorine oil and silicone oil. The content of these components in the hydrophobic liquid agent can be, for example, within the range of about 90 to 100% by weight, but is not limited thereto.

[0045] As the fluorine oil, a low polymer of a fluorine-containing monomer can be preferably used. For example, a low polymer of trifluorochloroethylene, perfluoropolyether, polytetrafluoroethylene, etc. can be mentioned. Depending on the molecular weight, there are light oils, medium oils, heavy oils, etc., and any of them can be used.

[0046] Examples of silicone oils include straight silicone oils such as dimethylpolysiloxane, methylphenylsilicone oil, and methylhydrogensilicone oil, as well as modified silicone oils such as reactive silicone oils and non-reactive silicone oils.

[0047] Examples of the reactive silicone oil include modified silicone oils such as amino-modified, epoxy-modified, carboxy-modified, carbinol-modified, methacryl-modified, phenol-modified, mercapto-modified, etc. Examples of the non-reactive silicone oil include modified silicone oils such as higher fatty acid-containing, higher fatty acid ester-modified, alkyl-modified, methylstyryl-modified, polyether-modified, etc.

[0048] In addition, other mineral oils, animal oils, vegetable oils, etc. may be contained within the range that does not impair the effects of the present invention. These may be publicly known or commercially available oils.

[0049] The viscosity of the hydrophobic liquid agent (25°C) is not particularly limited as long as it is liquid at room temperature and pressure and a predetermined liquid film is formed on the uneven surface. Generally, the viscosity is 100 to 10,000 mm 2 / s should be sufficient.

[0050] As described above, the hydrophobic liquid agent is present as a liquid film at least on the uneven surface of the base layer, but if the base layer has a porous structure, it is desirable that the hydrophobic liquid agent is also contained in the voids. By impregnating the voids in the base layer with the hydrophobic liquid agent, even if a part of the liquid film on the surface of the functional layer falls off together with ice blocks when the material of the present invention is used, the hydrophobic liquid agent contained in the voids of the base layer is supplied so as to seep out onto the surface of the base layer, so that the anti-icing effect can be maintained. It is sufficient if the hydrophobic liquid agent is distributed throughout the uneven parts of the base layer, but the fillers in the base layer may be entangled with each other to maintain the voids and bond to each other, thereby forming a three-dimensional network structure, and the hydrophobic liquid agent may be contained in the voids. As a result, even if the hydrophobic liquid agent on the uneven surface peels off or falls off as described above, the hydrophobic liquid agent present in the voids in the base layer can seep out onto the uneven surface due to capillary action or the like, thereby exhibiting a self-repairing effect.

[0051] The amount of the liquid film formed can be appropriately set depending on, for example, the desired anti-icing property, the type of hydrophobic liquid agent used, etc., but is usually 1.0 to 40 g / m 2 It is preferable to set the range to about that extent.

[0052] In addition, in the present invention, when the total amount of the organic binder, the filler of the present invention, and the hydrophobic liquid agent is 100% by weight, the respective proportions are not particularly limited, but it is preferable that the filler is about 8 to 60% by weight, the hydrophobic liquid agent is about 10 to 80% by weight, and the organic binder is about 30 to 90% by weight. In particular, when the content of the hydrophobic liquid agent is less than 10% by weight, the liquid film does not spread over the entire surface of the base layer, and sufficient anti-icing properties may not be obtained. In addition, when the content of the hydrophobic liquid agent is more than 80% by weight, the excess hydrophobic liquid film may flow out of the system without being fixed as a liquid film (fall off from the anti-icing material).

[0053] 2. Manufacturing method of anti-icing material The method for producing the material of the present invention is not limited, but it can be preferably produced by the following production method, that is, a method for producing an anti-icing material including a) a substrate and b) a functional layer formed on a surface of the substrate, (1) a step of preparing a coating material containing an organic binder and a filler having a core and a needle-shaped portion extending in at least two or more different directions from the core (a coating material preparation step); (2) applying the coating material to a substrate and drying the coating material to form a base layer (base layer forming step); and (3) forming a functional layer by applying a hydrophobic liquid agent onto the surface of the underlayer (functional layer forming step); It is possible to preferably employ a method for producing an anti-icing material, which is characterized by comprising the steps of:

[0054] Paint preparation process In the paint preparation step, a paint is prepared that contains an organic binder and a filler having a core and needle-like portions extending from the core in at least two or more different directions.

[0055] This is a process of preparing predetermined amounts of an organic binder, a filler, and a solvent, and mixing them. In other words, this is a process of preparing a coating material for forming a functional layer.

[0056] When preparing the coating material, an organic solvent may be used as necessary. The organic solvent effectively disperses the organic binder and the filler of the present invention, and allows the coating material to be applied uniformly to the substrate. The anti-icing material is preferably dried to remove the solvent, but a portion of the solvent may remain in the functional layer of the anti-icing material.

[0057] The organic solvent is not particularly limited, but examples thereof include aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, methylcyclohexane (MCH), ethylcyclohexane, and white spirit; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; ketones such as methyl ethyl ketone (MEK), ethyl isobutyl ketone, and methyl isobutyl ketone; and alcohols such as n-butanol and propyl alcohol. These organic solvents may be used alone or in combination of two or more.

[0058] Among these, it is preferable to use at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, ketones and esters, in order to more reliably obtain the material of the present invention.

[0059] The amount of organic solvent used in the coating material is generally preferably adjusted so that the solid content is about 1 to 30 mass %, but is not limited to this amount.

[0060] The mixing method may be any known method, for example, a mixer for mixing materials such as a rotation-revolution mixer, a planetary mixer, a mixing and defoaming machine, etc., which tilts a container containing the materials and rotates and revolves at high speed (movement like a planet revolving around the sun, planetary motion, planetary motion) to generate centrifugal force to generate material convection and shear stress to mix the materials, or a mixer such as a jet agitator or a high shear mixer, or ultrasonic waves can be used. Also, by combining these, it is possible to perform more uniform dispersion in a short time.

[0061] The ratio of the organic binder, filler, and solvent in the coating material is not particularly limited, and can be, for example, about 5 to 50% by weight of the filler, about 2 to 50% by weight of the organic binder, and the remainder being the organic solvent.

[0062] Base layer formation process In the undercoat layer forming step, the coating material is applied to a substrate and dried to form a coating film.

[0063] As described above, the material of the substrate is not particularly limited, and may be, for example, any of synthetic resins, rubber, metals, ceramics, fibrous materials (paper, nonwoven fabric, woven fabric, etc.), composite materials thereof, etc. The substrate may be any of products (finished products), semi-finished products, or raw materials thereof. The substrate may be applied to products (building materials, automobile parts, etc.) used outdoors for waterproofing, prevention of ice and snow, etc., or materials therefor.

[0064] The method of applying the coating material to the substrate is not limited, and can be carried out, for example, by a doctor blade, a bar coater, a brush, a roller, a spray gun, etc. In addition, in the present invention, when applying the coating material, the above-mentioned application and drying can be repeated two or more times to obtain a predetermined thickness.

[0065] The coating thickness of the coating material can be appropriately set depending on, for example, the use of the cured film, etc. For example, it can be adjusted so that the thickness of the cured film is about 0.1 to 50 μm, but is not limited thereto.

[0066] After the coating material is applied to the substrate, heat treatment is performed for drying to remove the solvent. The degree of heat treatment can be changed depending on the amount of coating material applied in the previous process, the amount of solvent contained in the coating material, etc. For example, it may be judged whether the solvent has completely evaporated by visual inspection, odor, etc. If the heat treatment is insufficient, there is a risk of poor curing. For this reason, when heat treatment is performed, it is desirable to perform it at about 50 to 160 ° C., but this is not limited. In addition, the heat treatment time may be set to a time sufficient for drying, and can be appropriately set depending on, for example, the heat treatment temperature, the type of substrate, etc.

[0067] Functional layer formation process In the functional layer forming step, a hydrophobic liquid agent is applied to the surface of the underlayer to form a functional layer. That is, this step can provide a functional layer in which a liquid film of the hydrophobic liquid agent is formed on the underlayer.

[0068] As the hydrophobic liquid, various hydrophobic liquids as described above can be used. In this case, an organic solvent or the like can be mixed as necessary.

[0069] The method of applying the hydrophobic liquid agent to the surface of the undercoat layer is not particularly limited, and can be carried out, for example, by immersion, a doctor blade, a bar coater, a brush, a roller, a spray gun, etc. In addition, in the present invention, when applying, the above-mentioned application and drying can be repeated two or more times to obtain a predetermined amount of liquid film formation.

[0070] The amount of the hydrophobic liquid to be applied is not particularly limited, but as described above, it is usually 1.0 to 40 g / m 2 By this step, a liquid film of the hydrophobic liquid agent is formed on the surface of the underlayer, thereby forming a functional layer.

[0071] 3. Use of the material of the present invention The material of the present invention can be applied to materials or articles that are used in environments where ice is likely to adhere to the surface.

[0072] Examples of embodiments of the material of the present invention include a) a method of using the material of the present invention by placing it on the surface of another material or article, and b) a method of using the surface component of an existing article as a base material and forming a functional layer on it.

[0073] The other material in a) is not particularly limited, and the material of the present invention can be applied to materials having various qualities, shapes, etc. The method of arrangement is also not limited, and it can be arranged and fixed on the surface of the other material using, for example, an adhesive, a pressure sensitive adhesive, a fixing member, etc.

[0074] In the method b), the article may be, for example, any of a part, a semi-finished product, a final product, etc. More specifically, the present invention can be suitably used for materials or articles that are mainly used outdoors, such as building materials or structures, such as roofs, wall materials, fences, posts, gutters, fences, culverts, street lights, traffic signals, electric bulletin boards, road signs, signs, vinyl greenhouses, steel towers, lighthouses, and guardrails; means of transport or vehicles, such as automobiles, bicycles, wheelchairs, ships, and aircraft; communication components, such as electric wires and antennas; and electrical devices, such as water heaters, outdoor units of air conditioners, and power generation devices (solar cells, wind power generation devices, etc.). EXAMPLES

[0075] The features of the present invention will be described in more detail below with reference to examples and comparative examples, although the scope of the present invention is not limited to the examples.

[0076] [Example 1] Thermoplastic paint mainly composed of polyolefin resin (Tanaka Chemical Co., Ltd., non-volatile content: 20% by weight, "290628-2 (prototype name)"), 10.0 parts by weight, needle-shaped zinc oxide crystal powder having a tetrapod shape (Panasonic, "Panatetra WZ-0501 (product name)"), 0.86 parts by weight, and mixed organic solvent (organic solvent in which MCH and MEK are mixed at a weight ratio of 1:1) were weighed out and mixed using a variable-rotation mixer (Mazerustar KK-400 (product name)) under conditions of rotation: 9, revolution: 9, and mixing time: 120 seconds to obtain a paint. The resulting paint was applied to a 25μm thick PET film using a #32 bar coater, and the organic solvent contained in the paint was evaporated by heating in an oven at 100℃ for 1 minute to obtain a film with a primer layer. At this time, about 14% voids were generated in the primer layer, and the unevenness of the surface of the primer layer was 5μm. A 10cm square backing plate was used on this film with the primer layer to obtain a 10cm square sample. Furthermore, this 10 cm square sample was immersed in silicone oil (Shin-Etsu Chemical Co., Ltd., "KF-96-100CS (product name)") for about 1 minute, then removed and left to stand at room temperature for one day and night (about 16 hours) while hanging vertically, and excess silicone oil was removed, and the silicone oil adhering to the back surface of the substrate was wiped off to obtain an anti-icing material sample. At this time, the amount of silicone oil was 50 mg per 10 cm square sample.

[0077] [Example 2] The anti-icing material sample was obtained in the same manner as in Example 1, except that the amount of the paint was changed and a mixture of 10.0 parts by weight of a thermoplastic paint mainly composed of polyolefin resin (Tanaka Chemical Co., Ltd., non-volatile content: 20% by weight, "290628-2 (prototype name)"), 2.0 parts by weight of zinc oxide having a tetrapod shape (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 8.0 parts by weight of a mixed organic solvent (an organic solvent in which MCH and MEK are mixed in a weight ratio of 1:1) was used. Note that about 32% of voids were generated in the base layer, the unevenness of the surface of the base layer was 8 μm, and the amount of silicone oil was 72 mg per 10 cm square sample.

[0078] [Example 3] The anti-icing material sample was obtained in the same manner as in Example 1, except that the paint composition was changed to use a mixture of 10.0 parts by weight of a thermoplastic paint mainly composed of polyolefin resin (Tanaka Chemical Co., Ltd., non-volatile content: 20% by weight, "290628-2 (prototype name)"), 4.7 parts by weight of zinc oxide having a tetrapod shape (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 18.7 parts by weight of a mixed organic solvent (an organic solvent in which MCH and MEK are mixed in a weight ratio of 1:1). The base layer had about 47% voids, the surface irregularities of the base layer were 14 μm, and the amount of silicone oil was 120 mg per 10 cm square sample.

[0079] [Example 4] The anti-icing material sample was obtained in the same manner as in Example 1, except that the amount of the paint was changed and a mixture of 10.0 parts by weight of thermoplastic paint mainly composed of polyolefin resin (Tanaka Chemical Co., Ltd., non-volatile content: 20% by weight, "290628-2 (prototype name)"), 17.9 parts by weight of zinc oxide having a tetrapod shape (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 71.4 parts by weight of a mixed organic solvent (an organic solvent in which MCH and MEK are mixed in a weight ratio of 1:1) was used. The base layer had about 63% voids, the surface irregularities of the base layer were 23 μm, and the amount of silicone oil was 140 mg per 10 cm square sample.

[0080] [Example 5] An anti-icing material sample was obtained in the same manner as in Example 3, except that silicone oil (Shin-Etsu Chemical Co., Ltd., "KF-96-1000CS (product name)") was used as the immersion oil. The base layer had voids of about 47%, the unevenness of the base layer surface was 14 μm, and the amount of silicone oil was 150 mg per 10 cm square sample.

[0081] [Example 6] An anti-icing material sample was obtained in the same manner as in Example 3, except that silicone oil (Shin-Etsu Chemical Co., Ltd., "KF-96-10000CS (product name)") was used as the immersion oil. The undercoat layer had voids of about 47%, the unevenness of the surface of the undercoat layer was 14 μm, and the amount of silicone oil was 340 mg per 10 cm square sample.

[0082] [Example 7] The anti-icing material sample was obtained in the same manner as in Example 1, except that the amount of the paint was changed and a mixture of 10.0 parts by weight of a thermoplastic paint mainly composed of polyolefin resin (Tanaka Chemical Co., Ltd., non-volatile content: 20% by weight, "290628-2 (prototype name)"), 4.0 parts by weight of zinc oxide having a tetrapod shape (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 16.0 parts by weight of a mixed organic solvent (an organic solvent in which MCH and MEK are mixed in a weight ratio of 1:1) was used. The base layer had about 51% voids, the surface irregularities of the base layer were 14 μm, and the amount of silicone oil was 110 mg per 10 cm square sample.

[0083] [Example 8] A solvent-based two-component curing silicone resin (Momentive Performance Materials Japan, LLC, non-volatile content: 30% by weight, "Release paper silicone TPR6722 (product name)") was used as the paint, and 10.0 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)") was used as the paint, and 6.0 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)"), 29.0 parts by weight of toluene, and 0.1 parts by weight of a curing agent (Momentive Performance Materials Japan, LLC, "CM670 (product name)") were used. An anti-icing material sample was obtained in the same manner as in Example 1. Note that about 50% of the voids were generated in the base layer, the unevenness of the surface of the base layer was 15 μm, and the amount of silicone oil was 110 mg per 10 cm square sample.

[0084] [Example 9] The anti-icing material sample was obtained in the same manner as in Example 1, except that the paint used was a mixture of 10.0 parts by weight of synthetic rubber (Tanaka Chemical Co., Ltd., non-volatile content: 15.7% by weight, "Synthetic Rubber 020907 (prototype name)"), 3.1 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 10.4 parts by weight of an organic solvent obtained by mixing toluene and methyl ethyl ketone in a weight ratio of 1:1. Note that about 47% of the voids were generated in the base layer, the unevenness of the surface of the base layer was 15 μm, and the amount of silicone oil was 110 mg per 10 cm square sample.

[0085] [Example 10] An anti-icing material sample was obtained in the same manner as in Example 1, except that the paint used was a mixture of 10.0 parts by weight of polystyrene thermoplastic elastomer (Sakuranomiya Chemical Co., Ltd., non-volatile content: 20% by weight, "SE-P1 (product name)"), 3.1 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 16 parts by weight of toluene. Note that approximately 45% of the base layer had voids, the unevenness of the base layer surface was 12 μm, and the amount of silicone oil was 105 mg per 10 cm square sample.

[0086] [Example 11] A liquid type thermoplastic polyurethane resin dimethylformamide doped (Okada Engineering Co., Ltd., non-volatile content: 15% by weight, "ARMH-9100-32 15% doped (DMF) (prototype name)") was used as the paint, and 10.0 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)") was used as the paint, 3.1 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)") and 9.5 parts by weight of dimethylformamide (DMF) were used. An anti-icing material sample was obtained in the same manner as in Example 1. Note that about 50% of the voids were generated in the base layer, the unevenness of the surface of the base layer was 14 μm, and the amount of silicone oil was 110 mg per 10 cm square sample.

[0087] [Example 12] An anti-icing material sample was obtained in the same manner as in Example 1, except that the paint used was a mixture of 10.0 parts by weight of polyurethane thermoplastic elastomer (Tanaka Chemical Co., Ltd., non-volatile content: 10% by weight, "Elastomer 020907-1 (prototype name)"), 2.0 parts by weight of tetrapod-shaped zinc oxide (Panasonic, "Pana-Tetra WZ-0501 (product name)"), and 3.0 parts by weight of a toluene / dimethylacetamide mixed solvent. The undercoat layer had voids of about 49%, the unevenness of the surface of the undercoat layer was 13 μm, and the amount of silicone oil was 110 mg per 10 cm square sample.

[0088] [Comparative Example 1] The film with the undercoat layer in Example 1 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0089] [Comparative Example 2] The film with the undercoat layer in Example 2 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0090] [Comparative Example 3] The film with the undercoat layer in Example 3 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0091] [Comparative Example 4] The film with the undercoat layer in Example 4 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0092] [Comparative Example 5] The film with the undercoat layer of Example 7 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0093] [Comparative Example 6] The film with the undercoat layer of Example 8 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0094] [Comparative Example 7] The film with the undercoat layer of Example 9 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0095] [Comparative Example 8] The film with the undercoat layer of Example 10 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0096] [Comparative Example 9] The film with the undercoat layer of Example 11 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0097] [Comparative Example 10] The film with the undercoat layer of Example 12 before immersion in silicone oil was used as an anti-icing material sample as it was.

[0098] [Test Example 1] The ice adhesion strength of each of the anti-icing material samples of the Examples and Comparative Examples was measured as follows. The anti-icing material sample was cut to about 20 mm x 40 mm, and if the back side of the film was wet with oil, it was wiped off with a cloth or the like, and the sample was placed on a slide glass (Matsunami Glass Industry S7224 (model number)) with the test surface facing up. Water was dripped between the anti-icing material sample and the slide glass to make them adhere to each other. Next, a disposable cell for measuring absorbance (capacity 4.5 mL, made of polystyrene) with a hole of about 2 mm at the bottom was placed upside down on the anti-icing material sample integrated with the slide glass, and cooled in a freezer at about -18 ° C for about 5 minutes. After about 5 minutes, 1.0 mL of water was poured into the hole in the disposable cell using a micropipette. Next, the sample was cooled in a freezer at about -18 ° C for about 6 hours, so that the anti-icing material sample and the slide glass were firmly adhered to each other with a layer of ice, and 1 cubic cm of ice was formed on the anti-icing material sample with a contact area of ​​1 square cm. The disposable cell with ice inside was placed in the freezer with a digital force gauge (IMADA DST-50N (product number)) and pressed against the cell to measure the force with which the ice peeled off the anti-icing material sample. This force was calculated based on the contact area of ​​the ice (0.0001 m2). 2 The ice adhesion strength (unit: kPa) was calculated by dividing the measured value by the average ice adhesion strength (unit: kPa). The results are shown in Table 1.

[0099] [Table 1]

[0100] As is clear from the results in Table 1, in Examples 1 to 12, the ice adhesion strength is about 1 / 10 compared to the Comparative Examples. Furthermore, in all of these Examples, the ice adhesion strength is an extremely small value of 20 kPa or less, which, as mentioned above, indicates a value that allows ice that has adhered due to natural wind and rain to be removed. In other words, the ice-proof material of the present invention is resistant to ice adhesion to its surface, or any ice that has adhered can be easily removed.

Claims

1. A material comprising: a) a substrate; and b) a functional layer formed on a surface of the substrate, (1) The functional layer comprises: (1a) an organic binder; a filler having a core portion and needle-like portions extending from the core portion in at least two or more different directions; a base layer having an uneven surface formed by the needle-like portions of the filler; and (1b) a surface layer formed on the uneven surface; (2) The surface layer is composed of a liquid film of a hydrophobic liquid agent. An anti-icing material characterized by:

2. An anti-icing material as described in claim 1, wherein the base layer has a porous structure and contains a hydrophobic liquid agent in the voids of the porous structure.

3. The anti-icing material described in claim 1, wherein the filler is an inorganic particle having needle-shaped portions extending from the core portion in four different axial directions.

4. The anti-icing material described in claim 1, wherein the hydrophobic liquid is at least one of silicone oil and fluorine oil.

5. An anti-icing material as described in claim 1, wherein the functional layer is 8 to 60% by weight of the filler and 10 to 80% by weight of the hydrophobic liquid film, with the entire functional layer being 100% by weight.

6. The anti-icing material described in claim 1, wherein the organic binder is at least one of resin, rubber, and elastomer.

7. A method for producing an anti-icing material comprising: a) a substrate; and b) a functional layer formed on a surface of the substrate, the method comprising: (1) a step of preparing a coating material including an organic binder and a filler having a core and needle-shaped portions extending in at least two or more different directions from the core; (2) applying the coating material to a substrate and drying it to form a base layer; and (3) forming a functional layer by applying a hydrophobic liquid agent to the surface of the underlayer; A method for producing an anti-icing material, comprising: