WO2002022758A1 - Revêtement glacé d'évacuation de la neige - Google Patents
Revêtement glacé d'évacuation de la neige Download PDFInfo
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- WO2002022758A1 WO2002022758A1 PCT/JP2001/008027 JP0108027W WO0222758A1 WO 2002022758 A1 WO2002022758 A1 WO 2002022758A1 JP 0108027 W JP0108027 W JP 0108027W WO 0222758 A1 WO0222758 A1 WO 0222758A1
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- snow
- coating
- water
- ice
- coating layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to outdoor structures such as structures in snowy and cold regions, such as traffic lights, road signs, gaze guidance signs, sound insulation walls, road safety structures such as protective fences, building structures such as roofs, outer walls, and fences, and telecommunication facilities.
- the present invention relates to a snow-snow clearing coating for preventing snow and ice on structures exposed to snow and ice in Japan. Itoda 1
- Snow accretion generated in snowy and cold areas causes various damages and obstacles to ordinary life and industrial activities. For example, if snow hits the wires, the wires will break or the tower will collapse, causing power outages over a wide area. In addition, snow that rolls up while the train is running may adhere to the panda graph and the underside of the vehicle, which may hinder the running of the train. In addition, snow and ice at places related to the recognition of the external situation, such as vehicle windows, may restrict or obstruct the driver's field of view, causing collisions with structures and traffic accidents.
- snow and ice when snow and ice arrive on road signs and bridges, the attached snow and ice gradually grows and increases in weight, and when the weight exceeds the adhesive force, it falls as a mass of snow and ice.
- snow and ice contain a small amount of water, the snow and ice grow to a considerably large weight due to the hydrogen binding force and van der Waals force derived from the water.
- the snow and ice blocks fall off road signs or bridges and fall, vehicles and pedestrians can pass under them, which can be catastrophic in some cases.
- Japanese Patent Application Laid-Open Nos. Hei 7-3131122, Hei 9-2790956, Japanese Patent Laid-Open No. Hei 10-88061, and Hei 11-2977228 As a method for preventing snow and ice, various inventions have been proposed in which a base material is coated with a water-repellent paint mainly containing a fluororesin or the like.
- a coating layer consisting of a super water-repellent film is formed on the outer surface of the base material by a method that improves the water-repellent performance of the paint to the utmost, and this coating layer prevents snow and ice from accumulating.
- the hydrogen bond and van der Waals force generated between the outer surface of the coating layer and snow and ice are the causes of snow and ice. They can be made smaller and try to prevent snow and ice.
- Japanese Patent Application Laid-Open No. H10-2373431 discloses a method in which photocatalyst fine particles are blended in a water-repellent coating layer, and contaminants adhering to the outer surface of the coating layer by the oxidation-reduction reaction are disclosed.
- a method has been proposed to maintain the super water repellency by decomposing and maintain the effect of preventing snow and ice.
- the water-repellent coating layer itself is decomposed simultaneously with contaminants by the redox reaction of the photocatalyst particles.
- the coating film itself deteriorates early, and the photocatalyst particles exposed on the outer surface of the coating layer become hydrophilic, which in turn leads to the problem of snow and ice.
- a water film is formed between the snow and ice and the outer surface of the coating layer when snow and ice begin to melt, and snow and ice slide down on the outer surface of the coating layer. That is, it can be expected that snow and ice attached by snow and ice will be removed from the outer surface of the coating layer.
- a super-water-repellent film does not form a water film on the outer surface due to its water repellency and is a discontinuous film having a large number of fine irregularities on the outer surface, so that snow and ice do not slide down smoothly.
- An object of the present invention is to provide a snow-sliding ice-like coating, and to provide a snow-sliding permanent coating which can be realized on a substrate by an inexpensive and simple method. Disclosure of the invention
- a snow-sliding coating corresponding to claim 1 of the present application is a snow-sliding coating formed on a surface of a base material and comprising a coating layer for preventing snow and ice,
- the outer surface of the coating layer is characterized by having a wettability with a contact angle of 70 ° or more with water and a water-sliding property with a sliding angle of water droplets of 40 ° or less.
- Invention 1 Corresponding to 1, hereinafter referred to as Invention 1).
- the snow and ice coating of the present invention is characterized in that the coating layer has a wettability with water of 70 ° or more and a water droplet sliding angle of 40 ° or less, so that the outer surface of the coating layer Snow and ice can be provided, snow and ice can be reduced, and attached snow and ice can be slid down.
- the snow-snow property refers to the ability to slide down while the part in contact with the outer surface of the snow-ice cover layer is kept constant, that is, the snow and ice slide while the sled slides on the snow surface. It is a property to drop. Snow and ice attached to a surface having snow and ice properties slides off the surface by its own weight when a small amount of water contained in the snow and ice intervenes between the surface and the snow and ice.
- the present invention by making the wettability of the outer surface of the coating layer with water at a contact angle of 70 ° or more, the ability of snow and ice to adhere to the outer surface of the coating layer, that is, due to the small amount of water contained in the snow and ice Control the hydrogen bonding force, van der Waals force, etc., and at the same time, the falling angle of the water droplets, that is, dropping the water droplets on the surface of the coating layer
- the angle of inclination to less than 40 degrees, snow and ice can slide down by their own weight due to the small amount of water contained in the snow and ice.
- the outer layer even when snow accretion occurs, the outer layer
- the snow and ice attached to the outer surface of the coating can be quickly slid off. Therefore, super-water-repellent water repellency is not required to prevent snow and ice, and the snow and ice that has adhered can be quickly slid down by an inexpensive and simple method, and the time during which the snow and ice are attached can be reduced as much as possible. Adhesion can be suppressed.
- the particles of the contaminants cannot be uniformly distributed on the entire outer surface of the coating layer.
- the condition of snow and ice is not significantly impaired.
- the coating film deteriorates, the coating performance decreases more gradually than the super water-repellent coating film, and the effect of preventing snow and ice can be maintained for a much longer period than that of the super water-repellent coating film.
- the outer surface of the coating layer of the present invention has a wettability with a contact angle with water of 70 ° or more, and preferably has a contact angle with water of 90 ° or more. If the contact angle is less than 70 degrees, the ability of a small amount of water contained in snow and ice to adhere to the outer surface of the coating layer cannot be reduced to a level that exhibits snow and ice properties. Further, the sliding angle of the water droplet is set to 40 degrees or less, preferably 30 degrees or less. If the sliding angle of the water droplet exceeds 40 degrees, it will be difficult for snow and ice attached to the outer surface of the coating layer to slide down due to its own weight.
- the outer surface of the coating has a water-sliding property, i.e., it has a property of sliding when water droplets move on the outer surface of the coating layer while maintaining a constant contact portion between the water droplets and the outer surface of the coating. is necessary. Fall, sand In other words, on the surface where water droplets move while rolling on the surface of the coating, the water contained in the snow and ice is extremely small and cannot be in the form of water droplets, and cannot move independently from snow and ice. You cannot expect sex.
- the coating layer preferably has a maximum surface roughness of 1 ⁇ or less (claim 2).
- the maximum surface roughness is the difference in microscopically uneven height on the outer surface of the coating layer.
- the ice frozen in the above temperature range is a coating layer which slides in a non-breaking manner under a constant load by a load from a direction horizontal to the coating layer (claim 3).
- the term “freezes” means that, for example, snow attached to the surface of the coating is once melted by the heat of the coating itself, and a water film is formed between the snow and the surface of the coating.
- the state in which the water film is cooled by the outside air temperature and is frozen is called “freeze", in which case snow freezes on the surface of the coating. In other words, this means “freezing” this water while the water and the surface of the coating are in contact.
- the maximum adhesion of snow and ice is in the temperature range of 12 ° C to 15 ° C in the outside air temperature. In this temperature range, the amount of water contained in the snow and ice is small but very large, and the adhesion of hydrogen and van der Waals forces derived from the water is also maximized, making snow and ice more likely to occur.
- the outside air temperature is lower than 15 ° C, the amount of water existing on the surface of snow and ice is small, and chemical adhesion is unlikely to occur. To fall off. Also, when the outside air temperature is higher than 12 ° C, the snowy state is not maintained and water droplets do not adhere to the outer surface. And slip down.
- Constant load non-breaking sliding means that frozen snow and ice slide on the outer surface of the coating without causing breakage of the icy joint at the interface with the outer surface of the coating due to gravity or external force acting on itself. . That is, when gravity or external force is applied, rather than suddenly breaking the frozen joint at a certain point and falling off the outer surface of the coating, the gravity or external force is applied from the point of time when the gravity or external force is applied at a certain point. This shows that snow and ice slide on the outer surface of the covering while maintaining the state. When snow and ice slide in a non-breaking manner with constant load, the snow and ice can be slid by gravity or external force smaller than the rupture of the frozen joint, and the snow and ice can easily slide down by their own weight.
- the coating layer is made of a substance exhibiting water repellency, and the substance is one or a mixture of two or more of a fluorine-containing silane compound, a fluorine-free silane compound and a fluorine-containing compound having a fluorocarbon group.
- Main component (Claim 4).
- This coating layer is a coating film containing the above-mentioned mixture as a main component.
- This coating film is formed by applying a coating liquid containing one or more of the above-mentioned mixtures as a main component, followed by drying and curing. Is done.
- the fluorine-free silane compound may have a methyl group (claim 5).
- This substance exhibiting water repellency can be formed by any water repellent, but does not adversely affect the polymer substrate when the substrate is made of a polymer such as synthetic resin which is vulnerable to heat. It is preferable to use a water-repellent substance that can form a film at a low temperature of 80 ° C. or lower and can be fixed to a hydroxyl group. As such a material, it is preferable to use a coating liquid mainly containing one or a mixture of two or more of the following substances.
- pitch fluoride (CFm m: 1.1 to 1.6 manufactured by Osaka Gas Co., Ltd.) or fluorinated resin, specifically polytetrafluoroethylene (PTFE), tetraethylene monohexafluoropropylene Copolymer (PFEP), Ethylene-tetrafluoroethylene copolymer (PETFE), Tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PEA), Polyvinylidene fluoride (PVd F), Polyfluorinated Such as Bull (PVF) Or a fluororesin coating agent based on them, or a fluorine-containing compound having a fluorocarbon group, or a fluororesin coating agent based thereon, or a fluorine-containing silane compound having a fluorocarbon group ⁇ Containing silane compounds 0
- the substance exhibiting the water repellency is uniformly distributed over 30% to 95% of the area of the entire outer surface of the substrate (Claim 6).
- the distribution of the water-repellent substance is 30% or less, it is difficult to increase the contact angle with water to 70 ° or more, and snow and ice cannot be reduced. On the other hand, if the distribution of the water-repellent substance is more than 95%, the balance of the force to adhere snow and ice will not be lost, and the snow and ice properties will not be obtained.
- the above-mentioned water-repellent substance is used as a coating liquid, for example, a dipping method, a spin coating method, a nozzle flow coating method, a spray method, a flow coating method, a brush coating method, a roller coating method. It can be applied by a method such as a wiping coating method or a combination of these methods.
- the diving method is preferable in that the uniformity of the film, the control of the film thickness and the like are easy and the smoothness for exhibiting the water-sliding property is obtained.
- the substance exhibiting water repellency is 30% to 95% of the area of the entire outer surface of the substrate. %, And a substance exhibiting water repellency is not distributed.
- a substance having hydrophilicity may be distributed on the outer surface of the substrate (claim 7).
- the following hydrophilic agent can be used for the substance having hydrophilicity, but the substrate itself may be made hydrophilic by using glass, metal oxide, or the like as the base material.
- . -As the hydrophilizing agent for example, RlaR2bR3cSiX4—a—b—c [R1, R2, R3: an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. a, b, c: '0-3. a + b + c: 0-3.
- X a hydroxyl group or a hydrolyzable functional group (halogen element, alkoxy group, isocyanate group)].
- a silica-based thin film is formed.
- a + b + c l, 2, 3 (R is a methyl group, an ethyl group, a phenyl group, etc.)
- the film is fired at a high temperature.
- Hydrocarbon group By firing and oxidizing R, a silica-based thin film can be obtained.
- a hydrophilic silica-based thin film can be obtained by applying the composition using a coating solution comprising a silicon coating agent based on the above-mentioned silane compound. .
- tetrachlorosilane, tetra-isocyanate silane, ethoxysilane triisocyanate and the like can be mentioned.
- a silicon coating agent based on these silane compounds may be used.
- the above-mentioned hydrophilic substance is used as a coating liquid, for example, a diving method, a spin coating method, a nozzle flow coating method, a spraying method, a flow coating method, a brush It can be applied by a coating method, a roller coating method, a wiping coating method, or a combination of these methods.
- the dipping method and the spraying method are preferable in that the uniformity of the film, the control of the film thickness and the like are easy and the smoothness for exhibiting the water-sliding property is obtained.
- the spray method it is preferable that the amount and pressure of the application liquid to be discharged are made as small as possible to suppress the progress of curing of the hydrophilizing agent and to form a uniform coating film.
- the material of the base material is not particularly limited, and it can be used regardless of whether it is inorganic or organic.
- Metal such as steel, stainless steel, aluminum alloy, zinc, synthetic resin, paper, wood, stone, glass, brick, pottery, Inorganic materials such as tiles may be used, and they may be coated with polyester resin, epoxy resin, urethane resin, etc., plated with zinc, aluminum, etc., alumite treatment, chromate treatment It may be one having been subjected to surface treatment or other surface treatment.
- the snow-sliding coating according to the present invention is a snow-sliding coating formed on a base material surface and comprising a coating layer for preventing snow and ice, wherein the outer surface of the coating layer has a surface tension of 3 ′. It is characterized by being a coating layer having a water repellency of 5 dyne / cm or less and a water drop sliding angle of 40 degrees or less (corresponding to claim 8, hereinafter referred to as invention 2).
- the force of snow and ice trying to adhere to the outer surface of the coating layer that is, the coating layer caused by a small amount of moisture existing on the surface of the snow and ice
- the coating layer caused by a small amount of moisture existing on the surface of the snow and ice
- snow and ice can slide down by their own weight due to a small amount of water contained therein by setting the sliding angle of water droplets to 40 degrees or less.
- the configuration of the present invention even when snow accretion occurs, snow and ice adhering to the outer surface of the coating can be quickly slid down due to the snow sliding durability of the outer surface of the coating layer. Therefore, it is not necessary to have super-water-repellent water repellency to prevent snow and ice, and the snow and ice that has adhered can be quickly slid down by an inexpensive and simple method, and the time during which snow and ice are adhered can be reduced as much as possible. However, it is possible to suppress the adhesion of snow and ice.
- the outer surface of the coating layer has the property that the water droplet slides down, that is, when the water droplet moves on the outer surface of the coating layer. It is necessary for the water droplet to move while the part where the water droplet contacts the outer surface of the coating is kept constant. Moisture on the surface of snow and ice is so small that it cannot be separated from snow and ice, and since there is almost no gap at the interface between snow and ice and the covering, moisture cannot be in the form of water droplets On the surface where water drops roll on the outer surface of the coating, it cannot be expected to have snow and ice properties due to its own weight. It is preferable that the surface tension is not more than 20 dyne / cm and the sliding angle of water droplet is not more than 30 degrees. In this case, more excellent snow and ice properties can be exhibited.
- the coating layer preferably has a water-sliding property such that water droplets slide on the outer surface of the coating layer at an advancing contact angle of 90 degrees or more, a receding contact angle of 50 degrees or more, and less than the advancing contact angle. Item 9).
- the advancing contact angle and receding contact angle when a water droplet slides down represent the balance between the water repellency of the outer surface of the coating layer and the bonding force between the molecules of the water droplet.
- the adhesion between the outer surface and the water droplets exceeds the bonding force between the molecules in the water droplets, making snow and ice more likely to occur.
- the receding contact angle is less than 50 degrees, snow and ice are likely to occur for the same reason as in the case of the advancing contact angle, and if the receding contact angle exceeds the advancing contact angle, the water droplets easily fall down and are hard to slide down. As a result, the snow and ice properties are reduced.
- the advancing contact angle is more preferably 100 degrees or more, and the receding contact angle is more preferably 60 degrees or more and the advancing contact angle is less, so that more excellent snow and ice properties can be exhibited.
- the coating layer preferably has a water-sliding property that allows the water droplets to slide down at a speed of 10 cm / min or less from the initial point of sliding down to 10 cm from the initial point of sliding down (claim 1). 0).
- a water-sliding property that allows the water droplets to slide down at a speed of 10 cm / min or less from the initial point of sliding down to 10 cm from the initial point of sliding down (claim 1). 0).
- a small amount of water existing on the surface is kept in stable contact with the interface between the snow and the outer surface of the coating layer, and water droplets are present in a physically unstable state on the outer surface of the coating layer. If it does, the moisture existing on the surface of snow and ice will not be in sufficient contact with the outer surface of the coating layer, and smooth snow and ice properties will not be exhibited.
- the water drop sliding speed is preferably 10 cm min or less, more preferably 5 cmZ min or less.
- the coating layer preferably has a maximum surface roughness of 1 ⁇ or less (claim 11). Since the operation and effect of this configuration are the same as those described in the description of the configuration corresponding to claim 2, the description is omitted here. Also, the coating layer is formed on the outer surface of the coating layer at a temperature of 12 ° C. It is preferable that the ice frozen in the temperature range of 5 ° C. slides in a constant load non-breaking manner by a load from the horizontal direction with respect to the coating layer (claim 12). The operation and effect of this configuration are also the same as those described in the description of the configuration corresponding to claim 1 above, and are not described here.
- the coating layer may be formed on an inorganic base film formed on a base material (claim 13).
- the inorganic base film By forming an inorganic base film on a substrate, the inorganic base film can be applied to any substrate or surface-treated such as coating or plating. By forming a coating layer thereon, it is possible to easily form a snow-and-ice coating layer on various substrates. Further, the inorganic base film functions as a hard coat layer, and can prevent the base material from being damaged.
- the inorganic base film may be a transparent film. With such an inorganic base film, it is possible to form a coating layer without impairing the appearance such as the color and gloss of the surface treatment film such as coating and plating.
- the inorganic base film has good adhesion to both organic and inorganic coatings, and its functional base material firmly fixes the water-repellent substance to make it snow- and ice-resistant and durable. It is possible to form a coating layer having high properties.
- the inorganic base film formed on the outer surface of the base material according to the present invention may be a metal oxide such as glass, titanium oxide, or alumina, and may be formed using them. Preferably, it is formed by using a silicon coating agent (claim 14).
- Silicon which is a main component of the silicon coating agent, has high adhesion to the above-described base material, and can well bond with the water-repellent substance.
- the silicon substances are bonded to each other by siloxane bonds similar to glass, and the film is extremely strong. Further, since the abundance of the silicon functional groups is high, the water-repellent substance can be easily and firmly fixed. It is also easy to form an inorganic base film.
- a known silicon coating agent for forming an inorganic base film containing silicon as a main component may be used.
- the coating method include a diving method, a spin coating method, a nose reflow coating method, and a spraying method. It can be applied by a flow coating method, a brush coating method, a roller coating method, a wiping coating method, etc., or a combination of these methods.
- the dipping method and the spraying method are preferable in that the uniformity of the film, the control of the film thickness and the like are easy, and the smoothness for exhibiting the water-sliding property is obtained.
- the coating layer is fixed on a base material with a water-repellent substance having a linear structure having a length of 5 or more members, with its terminals oriented to the outer surface of the coating layer. (Claim 15). Further, it is more preferable that the coating layer has a linear structure having a length of 1 OA or more. By immobilizing such a water-repellent substance having a linear structure, the sliding speed of water droplets on the outer surface of the coating layer can be reduced, and the water droplets can be made more water-slidable.
- the outer surface of the coating layer looks like a carpet with long hairs when viewed microscopically.
- this coating layer is viewed as a carpet, and the water-repellent substance having a linear structure is viewed as the hair foot of the carpet, if water drops are placed on the surface of the carpet, the water feet do not penetrate between the hair feet because the hair feet are water-repellent. It will be on an upright hairy foot. Carpet in this state When the entire body is tilted, the upright hair feet tilt in the direction of inclination due to the weight of the water drop, helping the water drop to start moving, and reducing the drop angle of the water drop. In addition, as the water droplets slide down the surface of the rugged carpet, the hairs on the trajectory incline one after another in the inclination direction, so that the water droplets can be kept down. This water droplet slides down without falling.
- the water-repellent material having a linear chain structure is much smaller than the particles of the contaminants, so that the contaminants do not penetrate into the coating layer, and thus are not applied to the outer surface. It is on the ground, and even if it adheres, it easily slides down with water droplets and snow and ice.
- the contaminants are only deposited on the outer surface of the coating layer, and do not prevent the water-repellent material having a linear structure from tilting, and do not lead to a decrease in snow-snow and ice properties. If the length of the water-repellent substance having a linear structure is less than 5 people, it will not be possible to incline sufficiently until snow-snow and ice properties are exhibited.
- a water-repellent substance having the following formula is more preferable because it tends to tilt more easily.
- the coating layer has a length of at least 5 members, more preferably at least 10 A, on the upper surface of the substrate, and has a linear structure having a trifluoromethyl group and / or a methyl group at the terminal. It is preferable that the aqueous material is fixed so that the terminal is oriented on the outer surface of the coating layer (claim 16).
- the trifluoromethyl group and the methyl group are functional groups having water repellency, and exhibit water repellency.
- a water-repellent substance having a linear structure in which a trifluoromethyl group is disposed at a terminal is fixed because the trifluoromethyl group is water-repellent, has high polarity as a functional group, and has a large functional group itself.
- the water-repellent substances having a straight-chained structure repel each other at the ends, so that they tend to be in an upright state, which is advantageous for snow-snow and ice properties.
- the density of the water-repellent material having a linear structure is repelled at the ends as described above, even when the density of the water-repellent material having a fixed linear structure is reduced due to deterioration with the passage of time, the density of the water-repellent material decreases.
- a water-repellent substance having a linear structure is unlikely to fall down, so that the period during which snow and ice can be exhibited can be lengthened, resulting in excellent durability.
- a water-repellent substance having a straight-chain structure in which a methyl group is located at the terminal is A water-repellent substance having a water-repellent group, a relatively small functional group and a linear structure can be densely fixed on the upper surface of the substrate.
- the linear structure is easy to move, and high snow and ice properties can be exhibited in the initial stage.
- Such a water-repellent substance having a straight-chain structure in which a trifluoromethyl group or a methyl group is arranged at the terminal may be used alone, or may be used as an appropriate mixture.
- one or more of the water-repellent substances having a linear structure are distributed substantially uniformly in 20 square persons (claim 17). If the area per substance is more than 20 square A, the number of hair feet is reduced when the above-mentioned coating layer is compared to a carpet and its hair feet, and the outer surface of the coating layer is as described above. Excellent snow and ice properties cannot be obtained.
- the water-repellent substance having a linear structure described above is fixed almost uniformly to 10 to 95% of the density at which the fixation of the water-repellent substance is saturated on the outer surface of the base material.
- the density at which the fixation is in the saturated state refers to the density in the maximum fixation state, although the density at which the water-repellent substance is microscopically fixed is limited by the size of the molecules and the intermolecular energy.
- the snow-ice generated between the two portions due to a small amount of water contained in the snow and ice and the outer surface of the coating layer can be separated.
- a difference occurs in the hydrogen bonding force, van der Waals force, etc. between the two, and this difference breaks the balance of the force of adhesion between snow and ice and the outer surface of the coating layer, and causes the water to move. Ice can be further promoted.
- the distribution of the water-repellent substance having a linear structure is less than 10%, the surface tension is reduced to 35 d It is difficult to make yne Z cm or less. On the other hand, if the distribution exceeds 95%, the effect of promoting snow-snow and ice cannot be achieved, because the balance between the forces that snow and ice tend to adhere to is not lost.
- the hydrophilic substance on a portion other than the portion where the water-repellent substance is distributed, that is, on the outer surface of the substrate on which the water-repellent substance is not fixed (claim 19).
- a greater difference in hydrogen bonding force, Van der Waals force, and the like is generated, so that the snow-snow and ice properties can be further improved.
- the hydrophilic substance makes it easier to wash away contaminants and other contaminants that adhere to the outer surface of the coating layer due to rainfall, etc.
- the coating layer in the above invention 2 is made of a material exhibiting water repellency, and the material is one or more of a fluorine-containing silane compound, a fluorine-free silane compound and a fluorine-containing compound having a fluorocarbon group. (Claim 20).
- This coating layer is a coating film containing the above mixture as a main component.
- This coating layer is formed by applying a coating liquid containing the above one plant or a mixture of two or more types as a main component, followed by drying and curing. Is done.
- the coating layer in the second aspect of the invention a substance exhibiting the same water repellency as in the first aspect of the invention is applied. Further, since the coating method is the same, the description is omitted here.
- These compounds are water-repellent substances having a linear structure and have a functional group with a high binding force, so that the coating layer can have good snow-snow and ice properties and can have durability.
- silicon and the above three types of water-repellent substances are bonded by siloxane bonds, and an extremely strong bonding force is obtained. It can be expressed and have excellent snow and ice resistance and durability.
- the fluorine-free silane compound preferably has a methyl group (claim 21).
- a water-repellent substance having a straight-chain structure in which a methyl group is located at the end has a relatively small methyl group functional group, and a water-repellent substance having a straight-chain structure is densely arranged on the upper surface of a substrate. Can be fixed, and the terminal functional group Because of its small size, the linear structure is easy to move, and high snow and ice properties can be exhibited at the initial stage.
- hydrophilic substance as in the above-described invention 1 is applied to the hydrophilic substance.
- FIG. 1 is a perspective view for explaining an apparatus for measuring a load required for sliding ice and a test for confirming a state of sliding ice
- FIG. 2 is a sectional view taken along line AA in FIG. . '.
- FIG. 3 is a diagram showing a model of the transition of the load by measuring the load required for the gliding ice and confirming the condition of the gliding ice, and shows the case of “breaking delamination”.
- FIG. 4 is a diagram showing a model of the transition of the load by measuring the load required for the gliding ice and confirming the state of the gliding ice, and shows a case of “constant load non-breaking sliding”.
- FIG. 5 is a table showing the results of an evaluation test and a snow and ice test of an example and a comparative example corresponding to the present invention 1.
- FIG. 6 is a table showing the results of evaluation tests and snow accretion tests of Examples and Comparative Examples corresponding to Invention 2. BEST MODE FOR CARRYING OUT THE INVENTION
- Example 8 Comparative Example 3 and Comparative Example 6, a glass plate having a size of 100 mm ⁇ 100 mm and a thickness of 1.5 mm was used as a coating base material or a measurement material.
- a polycarbonate plate coated with a silicon-based film having a thickness of 100 mm x 100 mm and a thickness of 3.0 mm was sufficiently subjected to corona discharge treatment, and the surface was activated (hydrophilic). ) To obtain a substrate.
- Example 1 Example 1
- ⁇ ⁇ ⁇ _24-9270 manufactured by Shin-Etsu Chemical Co., Ltd.
- a fluorosilicone coating agent was diluted to a solid content ratio of about 2.0% to obtain a coating solution for a water-repellent film.
- the polycarbonate plate was immersed in the coating liquid tank for a water-repellent film, pulled up at about 5 mm / min, dried at room temperature, and heat-treated at about 80 ° C for about 30 minutes. A coating was obtained.
- Example 2 The procedure was carried out except that the fluorosilicone coating agent X—24-7890 (Shin-Etsu Chemical Co., Ltd.) was diluted to a solid content of about 1.0% to obtain a coating solution for water-repellent films. In the same manner as in Example 1, the coating of Example 2 was obtained.
- a water-repellent film coating solution mainly composed of TSL8233 (manufactured by Toshiba Silicone Co., Ltd.), which is ptadecafluorodecyltriethoxysilane (FAS), and the mixing ratio of the water-repellent film coating solution the, C 8 F 17 C 2 H 4 S i (OC 2 H 5) 3: Echiru alcohol [E t OH]: water [0. 01 N, HN0 3] 1: 30: 2 as the back and forth, at room temperature The mixture was stirred for 5 hours to obtain a coating solution for a water-repellent film.
- TSL8233 manufactured by Toshiba Silicone Co., Ltd.
- FAS ptadecafluorodecyltriethoxysilane
- the polycarbonate plate is immersed in a coating solution tank for water-repellent film in an atmosphere with a relative concentration of about 10% or less, pulled up at a pulling speed of about 10 mmZ, dried at room temperature, and dried at room temperature. . (: About 30 minutes to obtain a coating of Example 4.
- Example 5 Using a coating solution for water-repellent film mainly composed of KB M7803 (Shin-Etsu Chemical Co., Ltd.), which is peptadecafluorodecyltrichlorosilane (HDFDTCS), , C 8 F 17 C 2 H 4 S i C 1 3: Shirikono i le (CF 994 manufactured by Shin-Etsu Chemical Co.) 1:99 to front and rear.
- the polycarbonate plate is immersed in the coating solution tank for water-repellent film for about 45 minutes in an atmosphere with a relative humidity of about 10% or less, dried at room temperature, and heat-treated at about 60 ° C for about 30 minutes.
- the coating of Example 5 was obtained.
- Example 6 A coating of Example 6 was obtained in the same manner as in Example 5, except that the polycarbonate plate was immersed in the coating liquid tank for a water-repellent film for about 20 minutes.
- Example 7 A coating of Example 7 was obtained in the same manner as in Example 5, except that the polycarbonate plate was immersed in the coating liquid tank for a water-repellent film for about 10 minutes.
- the coated article of Example 8 was obtained in the same manner as in Example 5, except that the glass plate as the coating substrate was sufficiently subjected to ultrasonic cleaning before being immersed in the coating liquid tank for the water-repellent film.
- a coating solution mainly composed of LS 2340 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is tetraethoxysilane (TEOS), is used.
- the polycarbonate plate is immersed in the coating solution tank for hydrophilic film in an atmosphere with a relative humidity of about 10% or less, pulled up at a pulling speed of about 10 mm / min, dried at room temperature, and dried at about 60 ° C.
- Black mouth trifluoroethylene fluororesin (Zaflon FC110 manufactured by Toa Gosei Co., Ltd.) '40 parts by weight, xylene: toluene: ethyl acetate: methyl ⁇ isobutylketone in a ratio of 3: 1: 1: 1
- the mixture was dissolved in the mixed solvent and stirred at room temperature for 20 minutes. Thereafter, 5 parts by weight of an isocyanate curing agent (Coronate 2515 manufactured by Toagosei Co., Ltd.) was added, and the mixture was further stirred for 10 minutes to obtain a coating solution for a water-repellent film.
- Example 10 A coating of Example 10 was obtained.
- Anoreminiumu 3 6 0 _ Putokishido [1 (O- sec-Bu) 3] and the iso-propyl alcohol [IPA], After stirring for about 1 hour at room temperature, was added Aseto acetic acid Echiru [EAc Ac], about 1 Stirred for hours. Thereafter, water [0. 0 IN, HN0 3] isopropyl alcohol Honoré [IPA] was added, with Mo / Les ratio, A 1 (0- sec -Bu) 3: I PA: EA cAc: 0. 0 IN, HN_ ⁇ 3 1: 30: 1: 2 ratio, to prepare a coating solution of the transparent ⁇ alumina film for forming an alumina sol solution was stirred for about 5 hours.
- the polycarbonate plate was immersed in the adjusted coating solution for forming a transparent alumina film, and then pulled up at a speed of about 30 Omm / min to form a coating film on the polycarbonate plate. After curing at room temperature for about 30 minutes, immersing it in warm water at about 80 ° C for about 30 minutes, then pulling it out of the immersion tank, and drying it at room temperature for about 60 minutes to obtain a polycarbonate plate with a transparent alumina thin film Was. Next, a fluorosilicone coating agent KP-801M (manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to a solid content ratio of about 0.5% to obtain a coating solution for a water-repellent film.
- a fluorosilicone coating agent KP-801M manufactured by Shin-Etsu Chemical Co., Ltd.
- the polycarbonate plate with the transparent alumina thin film was sufficiently subjected to corona discharge treatment, and was immersed in the water-repellent film coating liquid tank when the contact angle with water reached about 3 degrees. After raising at a rate of about 5 mm / min, drying at room temperature, and heat-treating at a temperature of about 60 ° C. for about 30 minutes, a water-repellent film was formed on the petal-shaped transparent alumina thin film to obtain a coating of Comparative Example 1.
- a fluorosilicone coating agent KP-801M (manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to a solid content of about 0.5% to obtain a coating solution for a water-repellent film.
- the polycarbonate plate was immersed in the coating solution bath for water-repellent film, pulled up at about 5 mm / 7 minutes, dried at room temperature, and heat-treated at about 60 ° C for about 30 minutes. Obtained cover.
- a coated product of Comparative Example 3 was obtained in the same manner as in Comparative Example 2, except that the glass plate as the coating substrate was sufficiently subjected to ultrasonic cleaning before being immersed in the coating liquid tank for the water-repellent film.
- a glass plate that is not particularly treated is used.
- the area occupancy of the water-repellent substance was measured by a molar ratio using an X-ray photoelectron spectrometer (ESCA5400, manufactured by ULVAC FAI). Calculated based on Furthermore, the water repellency and the water slip were measured for each of these Examples and Comparative Examples.
- the water repellency was determined by measuring the contact angle of each coating with a water droplet in the air using a contact angle meter.
- the water slip was measured by dropping a water drop on the outer surface of each coating, gradually stopping the water drop, and then gradually inclining the coating.When the water droplet began to move on the outer surface of the coating, the outer surface of the coating and the horizontal surface were measured.
- the sliding speed is calculated by measuring the distance and time required for a water droplet to move between arbitrary points after moving on the outer surface of the coating.
- FIG. 1 is a perspective view for explaining the test apparatus
- FIG. 2 is a cross-sectional view taken along line AA in FIG.
- FIG. 3 shows the case where the load disappears at a stroke 51 at the time when the icing starts to move, and is expressed as "fracture peeling".
- Fig. 4 shows the case where the load at the point 61 when the icing began to move remains the same, and is expressed as "constant load non-breaking sliding".
- the coatings of each of these Examples and Comparative Examples were installed at the same point in Hokkaido in winter and at the same time, and a snow ice test was performed to confirm the actual degree of snow water.
- the covering is installed so that its outer surface is perpendicular to the ground surface.
- the degree of snow and ice is represented by the rate of snow and ice, and the lower the value is, the more difficult it is to determine snow-ice resistance (snow-ice properties).
- the snow-covered water rate is calculated by using the time during which snow and ice are observed on each sample as the snow-and-ice time and the time during which precipitation such as snow and rain is observed as the total precipitation time.
- the water has a wettability with a contact angle of 70 ° or more, preferably 90 ° or more with water, and a water droplet slides down at a slip angle of 40 ° or less, preferably 30 ° or less. It has been shown that the outer surface of the coating layer has an excellent snow sliding property and has an effect of preventing snow and ice.
- the outer surface of the coating layer with a smoothness of not more than 10 ⁇ , preferably not more than 1 ⁇ , a more excellent snow and ice prevention effect is exhibited.
- Table 1 the evaluation test was performed with ice frozen at 15 ° C. The results of this evaluation test are consistent with the snow and ice properties under actual installation conditions, and the ambient air temperature was 12 ° C.
- the effect of the coating layer on the prevention of snow and ice can be determined by the snow and ice properties of snow and ice frozen at C to 15 ° C, preferably 15 ° C.
- a 100 mm X 100 mm, 8 mm thick aluminum plate is chromate-treated, and its outer surface is spray-coated with an epoxy resin-based primer, heat-cured at about 150 ° C for 30 minutes, and further cured.
- Spray paint with urethane resin paint on the outer surface heat and cure at about 150 ° C for 30 minutes, and then spray paint with silicone coating agent KP854 (Shin-Etsu Chemical Co., Ltd.) on the outer surface. After drying the solvent at room temperature, it is heated and cured at about 100 ° C. for 30 minutes, and the base material is formed by forming an inorganic base film on a urethane-coated aluminum plate.
- Example 11 of the present invention The same coating liquid for forming a coating layer as used in Example 1 was spray-coated on this inorganic base film with the discharge amount and discharge pressure as low as possible, and the solvent was dried at room temperature. Heat treatment was performed at about 80 ° C. for 30 minutes to obtain a coating of Example 11 of the present invention.
- Example 11 a coating material of Example 12 was obtained in the same manner as in Example 11, except that the coating liquid for forming the coating layer used in Example 2 was used. '[Example 13]
- Example 11 the coating liquid for forming the coating layer used in Example 3 was used, and the amount and discharge pressure of this coating liquid were reduced as much as possible in an atmosphere having a relative humidity of about 10% or less. Then, spray coating was performed on the inorganic base film on the same substrate as that used in Example 11 and the solvent was dried at room temperature, followed by heat treatment at about 60 ° C for 30 minutes. Thus, the coating of Example 13 was obtained.
- Example 11 the coating liquid for forming the coating layer used in Example 4 was used, and the discharge amount and the discharge pressure of this coating liquid were reduced as much as possible in an atmosphere having a relative humidity of about 10% or less. Then, spray coating was performed on the inorganic base film on the same substrate as that used in Example 11 and the solvent was dried at room temperature, followed by heat treatment at about 60 ° C for 30 minutes. Thus, a coating of Example 14 was obtained.
- Example 11 the coating liquid for forming the coating layer used in Example 5 was used. Then, in an atmosphere having a relative humidity of about 10% or less, the coating amount and the discharging pressure of this coating liquid were made as low as possible, and the inorganic base on the same substrate as used in Example 11 was used. Spray coating on the film and drying of the solvent at room temperature were repeated 5 times, and then heat-treated at about 60 ° C. for 30 minutes to obtain a coating of Example 15.
- Example 15 the coating liquid for forming the coating layer was spray-coated on the same inorganic base film on the same base material as used in Example 11 with the discharge amount and the discharge pressure as low as possible.
- the coating of Example 16 was obtained in the same manner except that the drying of the solvent at room temperature was repeated three times.
- Example 15 the coating liquid was discharged and the discharge pressure was reduced as much as possible, and the inorganic base film on the same substrate as used in Example 11 was spray-coated, and the solvent was removed at room temperature.
- a coating of Example 17 was obtained in the same manner except that drying was repeated twice.
- Example 9 The same coating liquid as that used in Example 9 was used as the coating liquid for forming the hydrophilic film, and the discharge amount and discharge pressure of this coating liquid were reduced as much as possible in an atmosphere having a relative humidity of about 10% or less. Then, the inorganic base film on the same substrate as that used in Example 11 was spray-coated, the solvent was dried at room temperature, and then heat-treated at about 60 ° C for 30 minutes to form an outer surface. A coated plate on which a hydrophilic film was formed was obtained. Next, using the coating liquid for forming the coating layer used in Example 9, in an atmosphere having a relative humidity of about 10% or less, the discharge amount and the discharge pressure of this coating liquid were reduced as much as possible. The outer surface of the coated plate was spray-coated and the solvent was dried at room temperature five times, and then heat-treated at about 60 ° C. for 30 minutes to obtain a coating of Example 18.
- a coating solution for the coating a coating solution containing alkylsilane KBM_7103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the main component is used.
- Example 19 In an atmosphere having a relative humidity of about 10% or less, the discharge amount and the discharge pressure of this coating liquid were reduced as much as possible, and the inorganic base film on the same substrate as used in Example 11 was used. After spray-coating on it and drying the solvent at room temperature, it was heat-treated at about 60 ° C. for 30 minutes to obtain a coating of Example 19.
- Example 11 The same coating liquid for forming a coating layer as that used in Comparative Example 2 was used in an atmosphere having a relative humidity of about 10% or less, and the amount and pressure of this coating liquid were reduced as much as possible. Spray-coated on the same inorganic base film on the same base material as used in the above, dried the solvent at room temperature, and heat-treated at about 60 ° C for 30 minutes to obtain the coating of Comparative Example 6a. I got
- a 100 mm X 100 mm, 0.8 mm thick aluminum plate is chromate-treated, and its outer surface is spray-coated with an epoxy resin-based primer and heat-cured at about 150 ° C for 30 minutes. Further, a urethane resin-based paint is spray-coated on the outer surface, and the base material is a urethane-coated aluminum plate which is heated and cured at about 150 ° C. for 30 minutes.
- the same coating liquid for forming a coating layer as that used in Example 5 in an atmosphere having a relative humidity of about 10% or less, the discharge amount and the discharge pressure of this coating liquid were reduced as much as possible. Spray coating the substrate and drying the solvent at room temperature were repeated 5 times, followed by heat treatment at about 60 ° C. for 30 minutes to obtain a coating of Comparative Example 7.
- Example 11 The same coating liquid for forming a coating layer as used in Comparative Example 4 was discharged onto the inorganic base film on the same base material as used in Example 1 with the discharge amount and the discharge pressure as low as possible. Spray coating was performed and the solvent was dried at room temperature to obtain a coating of Comparative Example 8.
- Example 11 The same coating liquid for forming a coating layer as that used in Comparative Example 5 was discharged onto the inorganic base film on the same base material as that used in Example 1 with the discharge amount and discharge pressure as low as possible.
- the coating of Comparative Example 9 was obtained by spray coating and drying the solvent at room temperature. (Comparative Example 10).
- Example 11 On the same inorganic base film as that used in Example 11 on the same inorganic base film, the same coating liquid for forming the coating layer as used in Example 10 was discharged and the discharge pressure as low as possible. Then, the solvent was dried at room temperature, and then heat-treated at about 100 ° C. for 30 minutes to obtain a coating of Comparative Example 10.
- Example 15 was repeated in the same manner as in Example 15 except that spray coating was performed on the same inorganic base film as that used in Example 11 and the solvent was dried at room temperature only once. Thus, the coating of Comparative Example 11 was obtained.
- a 100 mm X 100 mm, 0.8 mm thick aluminum plate is chromate-treated, and its outer surface is spray-coated with an epoxy resin-based primer and heat-cured at about 150 ° C for 30 minutes. Furthermore, a urethane-coated aluminum plate spray-coated on its outer surface and heat-cured at about 150 ° C for 30 minutes is used. (Comparative Example 13)
- the surface tension was measured by measuring the leak index of the reagent in the atmosphere on the outer surface of each coating by the method described in JIS K 678. The surface tension was measured before and after the snow and ice test in Hokkaido. The advancing contact angle and the receding contact angle were measured by recording the state of the water droplet moving on the outer surface of the coating with a video camera, and observing the recorded image just before the water droplet started moving.
- the length of the water-repellent material having a linear structure in each of these Examples and Comparative Examples was estimated from the molecular weight of the main component forming the coating layer in the coating liquid for forming the coating layer.
- the area occupancy was determined by measuring the molar ratio with an X-ray photoelectron spectrometer (ESCA540, manufactured by ULVAC-FAI), and calculating based on the measured value.
- the density of the water-repellent material having a straight-chain structure fixed on the surface was determined as a ratio to the density at which the material becomes saturated.
- the methods for measuring the water slippage, sliding speed, maximum surface roughness, ice peeling or the load required for slipping, checking the state of ice peeling and slipping, and the rate of snow accretion and ice deposition are as described in the above Invention 1.
- the method is the same as that performed for the comparative example, and the description is omitted here.
- the total precipitation time in this snow accretion test is about 1000 hours, and most of the time is due to snowfall.
- the rate of snow and ice is less than 10%, it can be evaluated as an excellent snow and ice resistant coating.
- the coatings in Examples 1 to 19 having an outer surface with a surface tension of 35 dyne / cm or less and a sliding angle of water droplets of 40 ° or less have a low snow / ice rate. The results are shown. Therefore, it has been shown that the outer surface of the coating layer in the present invention has excellent snow-snow and ice properties, and has an excellent effect of preventing snow and ice.
- Comparative Examples 7 and 10 each had an outer surface with a surface tension of SS dyne / cm or less and a sliding angle of water droplets of 40 degrees or less, but in Comparative Example 7, a polyurethane resin was used.
- a coating layer having snow and ice properties is directly coated on the base coating film, and a strong siloxane bond as shown in the present example cannot be obtained.
- the coating layer falls off from the base material, and the coating layer cannot exhibit snow and ice properties. For this reason, the rate of snow and ice ultimately is slightly higher at 15%.
- the falling of the water-repellent substance causes the coating layer to deteriorate, and the difficulty in snow and ice resistance becomes noticeable at an early stage.
- Comparative Example 10 is As shown in the table, the length of the linear-structured water-repellent material is three, and the rate of snow and ice eventually reaches 15%, which is slightly higher. From the viewpoint of the length of the water-repellent substance having this linear structure, Examples 1 to 19 are all 5 A or more, and a high rate of snow and ice is obtained.
- Examples 1 to 19 which exhibited high resistance to snow and ice, water droplets slipped on the outer surface of the coating, and as in Comparative Examples 1 to 6, and Comparative Examples 8, 9 12 In all cases, the rate of snow and ice accumulation is as high as 30 to 60%.
- Examples 1 to 19 are included in the range of the present invention, with respect to the point that the advancing contact angle of the water droplet sliding down is set to 90 degrees or more and the receding contact angle is set to 50 degrees or more and equal to or less than the advancing contact angle. This is consistent with the snow and ice properties of the actual installation situation.
- the fact that the sliding speed of water droplets is not more than 10 cmZ is also included in this example in all of Examples 1 to 19, which is consistent with the snow and ice properties in actual installation conditions. .
- the area occupancy of the water-repellent material was 8% in Comparative Example 11 and the surface tension was 39 dyne / cm, and the area occupancy of the water-repellent material, that is, It is shown that the surface tension does not decrease sufficiently when the ratio of the saturated density to the fixed density is less than 10%.
- the snow accretion ratio was slightly higher in Comparative Example 11 at 20%.
- the surface tension after the snow accretion test 100 It is slightly higher than the initial one, and there is almost no change. As a result, it is shown that the degree of snow-ice and ice-related deterioration due to the adhesion of pollutants and the deterioration of the coating layer is small, and that snow-and-ice resistance can be maintained for a long period of time. From the above results, the snow-and-ice coverings of the present inventions 1 and 2 can quickly slide down the snow and ice attached to the outer surface of the covering layer even when they have snow and ice due to the snow and ice properties of the outer surface of the covering layer. it can.
- the attached snow and ice can be quickly slid down by the coating layer formed by a relatively inexpensive and simple method without requiring super-water-repellent water repellency to prevent snow and ice.
- Snow and ice adhesion can be controlled, for example, by shortening the snow and ice adhesion time as much as possible.
- the particles of the contaminants cannot be uniformly distributed on the entire outer surface of the coating layer. Since the parts with snow and ice properties are exposed, the snow and ice properties are not significantly impaired. Furthermore, the contaminants are removed along with the snow and ice sliding down the outer surface of the coating, so that they do not accumulate on the outer surface of the coating.
- the snow- and ice-based covering according to the present invention includes: a tunnel entrance, a central separating strip railing, a sound-insulating wall cap, a truss of a truss bridge, a sign board, a snow cover, a sign, a mirror, a self-luminous body, Shelter, bicycle shed, lighting, arbor, wind-proof snow shelves, anti-floating fences, housing roof snow eaves prevention boards, housing roof parapets, solar batteries, blinds for home verandas, shelves and garbage dumps It is formed on the outer surface of an outdoor work where there is a concern that the structure or the like may be adversely affected by snow and ice, and is suitably used.
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/380,317 US20040038046A1 (en) | 2000-09-14 | 2001-09-14 | Snow sliding icy coating |
CA 2422101 CA2422101A1 (en) | 2000-09-14 | 2001-09-14 | Snow sliding icy coating |
EP20010967689 EP1323805A1 (en) | 2000-09-14 | 2001-09-14 | Snow sliding icy coating |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-279653 | 2000-09-14 | ||
JP2000279653A JP3848527B2 (ja) | 2000-09-14 | 2000-09-14 | 滑雪氷性被覆物 |
JP2001-103031 | 2001-04-02 | ||
JP2001103031A JP2002294226A (ja) | 2001-04-02 | 2001-04-02 | 滑雪氷性被覆物 |
Publications (1)
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WO2002022758A1 true WO2002022758A1 (fr) | 2002-03-21 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/JP2001/008027 WO2002022758A1 (fr) | 2000-09-14 | 2001-09-14 | Revêtement glacé d'évacuation de la neige |
Country Status (5)
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US (1) | US20040038046A1 (ja) |
EP (1) | EP1323805A1 (ja) |
CN (1) | CN1458971A (ja) |
CA (1) | CA2422101A1 (ja) |
WO (1) | WO2002022758A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002180035A (ja) * | 2000-12-08 | 2002-06-26 | Sekisui Jushi Co Ltd | 滑雪氷性被覆物 |
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US7567991B2 (en) * | 2003-06-25 | 2009-07-28 | Emc Corporation | Replication of snapshot using a file system copy differential |
JP2008233878A (ja) * | 2007-02-20 | 2008-10-02 | Hoya Corp | 防塵性反射鏡及びそれを具備する光学系装置 |
US20120149814A1 (en) * | 2009-08-19 | 2012-06-14 | Jinyong Li | Ultrahydrophobic coating and method for making the same |
CN101817980B (zh) * | 2010-04-22 | 2012-05-23 | 复旦大学 | 一种氧化硅超疏水薄膜的溶胶凝胶制备方法 |
US8765228B2 (en) * | 2011-12-02 | 2014-07-01 | Ppg Industries Ohio, Inc. | Method of mitigating ice build-up on a substrate |
CN103162304B (zh) * | 2011-12-13 | 2016-03-09 | 河南省电力勘测设计院 | 烟囱筒首自动化冰装置及其化冰方法 |
US20160333510A1 (en) | 2015-05-13 | 2016-11-17 | Milliken & Company | Non-woven underbody shield |
CN107099273B (zh) * | 2017-05-22 | 2023-06-30 | 张兆国 | 仿生自响应防冰雪自清洁材料和应用 |
US10611116B2 (en) | 2018-05-17 | 2020-04-07 | Milliken & Company | Nonwoven composite |
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- 2001-09-14 CN CN01815702A patent/CN1458971A/zh active Pending
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JP2000144121A (ja) * | 1998-11-09 | 2000-05-26 | Ikuo Narisawa | 表面処理剤、これを用いた水滴滑落性基材及びその製造方法 |
JP2000144056A (ja) * | 1998-11-10 | 2000-05-26 | Ikuo Narisawa | 水滴滑落性に優れた表面処理基材及びその製造方法 |
JP2000230060A (ja) * | 1999-02-15 | 2000-08-22 | Showa Highpolymer Co Ltd | 滑水性高分子組成物皮膜 |
JP2000239601A (ja) * | 1999-02-22 | 2000-09-05 | Kansai Paint Co Ltd | 滑水性表面を形成し得るポリマー組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002180035A (ja) * | 2000-12-08 | 2002-06-26 | Sekisui Jushi Co Ltd | 滑雪氷性被覆物 |
Also Published As
Publication number | Publication date |
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CN1458971A (zh) | 2003-11-26 |
CA2422101A1 (en) | 2003-03-11 |
US20040038046A1 (en) | 2004-02-26 |
EP1323805A1 (en) | 2003-07-02 |
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