WO2022202990A1 - 放射冷却装置 - Google Patents
放射冷却装置 Download PDFInfo
- Publication number
- WO2022202990A1 WO2022202990A1 PCT/JP2022/013947 JP2022013947W WO2022202990A1 WO 2022202990 A1 WO2022202990 A1 WO 2022202990A1 JP 2022013947 W JP2022013947 W JP 2022013947W WO 2022202990 A1 WO2022202990 A1 WO 2022202990A1
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- WIPO (PCT)
- Prior art keywords
- layer
- resin material
- cooling device
- radiative cooling
- material layer
- Prior art date
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Images
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Definitions
- the present invention comprises an infrared emitting layer that emits infrared light from an emitting surface, and a light reflecting layer that is positioned on the opposite side of the infrared emitting layer from the side where the emitting surface exists,
- the present invention relates to a radiative cooling device, wherein the infrared radiation layer is a resin material layer having a thickness adjusted to emit thermal radiation energy larger than absorbed solar energy in a wavelength band of 8 ⁇ m to 14 ⁇ m.
- Radiative cooling is a phenomenon in which the temperature of a substance is lowered by radiating electromagnetic waves such as infrared rays to its surroundings. By utilizing this phenomenon, for example, it is possible to construct a radiative cooling device that cools an object to be cooled without consuming energy such as electricity. Further, since the light reflecting layer sufficiently reflects sunlight, it is possible to cool the object to be cooled even in a daytime sunlight environment.
- the light reflecting layer reflects the light (ultraviolet light, visible light, infrared light) that has passed through the infrared emitting layer and emits it from the emitting surface, and the light that has passed through the infrared emitting layer (ultraviolet light, visible light).
- the light reflection layer also has the function of reflecting the light emitted from the infrared radiation layer toward the side where the light reflection layer exists toward the infrared radiation layer.
- the purpose of providing the light reflecting layer is to reflect the light (ultraviolet light, visible light, infrared light) transmitted through the infrared radiation layer.
- the radiative cooling device it is desired to reduce the cost of the resin material layer in order to reduce the cost of the radiative cooling device. Also, in order to provide flexibility to the radiative cooling device, it is desirable to soften the resin material layer. In other words, if the light reflection layer is configured as, for example, a silver thin film to provide flexibility, and the resin material layer that configures the infrared radiation layer is provided with flexibility, the radiative cooling device can be made flexible. will be provided. It is desired to improve the weather resistance at the same time as providing the flexibility. If the radiative cooling device has flexibility and weather resistance in this way, it can be retrofitted to the outer walls of existing outdoor facilities to provide radiative cooling performance, thereby improving convenience.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a radiative cooling device which can be made flexible while achieving cost reduction and which can improve weather resistance. be.
- the radiative cooling device of the present invention comprises an infrared radiation layer that emits infrared light from a radiation surface, and a light reflection layer that is positioned on the side of the infrared radiation layer opposite to the radiation surface.
- the infrared radiation layer is a resin material layer having a thickness adjusted to emit thermal radiation energy greater than the absorbed solar energy in a wavelength band of 8 ⁇ m to 14 ⁇ m, characterized by:
- the resin material forming the resin material layer is a vinyl chloride resin mixed with a plasticizer,
- the plasticizer is composed of one or more compounds selected from the group consisting of phthalates, aliphatic dibasic esters and phosphate esters.
- the vinyl chloride resins used in the present invention are vinyl chloride or vinylidene chloride homopolymers and vinyl chloride or vinylidene chloride copolymers, and are produced by conventionally known polymerization methods.
- the vinyl chloride-based resin provides sufficient heat radiation in the window region of the atmosphere.
- vinyl chloride resin has the same heat radiation characteristics as fluororesin and silicone rubber, which can obtain large heat radiation in the window area of the atmosphere. It is effective in constructing a radiative cooling device in which the temperature is lower than that at a low cost.
- the vinyl chloride resin contains a plasticizer, the resin material layer has flexibility, and as a result, the radiative cooling device has flexibility.
- vinyl chloride resin becomes soft by adding a plasticizer, so even if it comes into contact with other objects, it will flexibly change its shape to avoid damage, so it can be used for a long time. can be maintained in a beautiful state.
- the thin film-like fluororesin is hard, it cannot be flexibly changed in shape by contact with other objects, and is easily scratched, making it difficult to maintain a beautiful state.
- a plasticizer to the vinyl chloride resin, even if it is scratched, it can be deformed by heating to 80 ° C. or higher to eliminate the surface scratches and smooth it, that is, the scratches can be self-repaired. Fluororesins and silicone rubbers do not have this characteristic.
- the plasticizer mixed in the vinyl chloride resin is one or more compounds selected from the group consisting of phthalates, aliphatic dibasic esters and phosphate esters, the plasticizer is the sun Since it becomes difficult to absorb ultraviolet light (ultraviolet light with a wavelength of 295 nm to 400 nm) contained in light, the weather resistance of vinyl chloride resin mixed with a plasticizer can be improved. In other words, when the plasticizer mixed in the vinyl chloride resin absorbs ultraviolet rays, the hydrolysis of the plasticizer progresses, resulting in dehydrochlorination of the vinyl chloride resin and the resulting coloring (brown). However, since the plasticizer does not easily absorb the ultraviolet rays contained in the sunlight, the weather resistance of the vinyl chloride resin mixed with the plasticizer can be improved.
- the radiative cooling device of the present invention it is possible to provide a radiant cooling device that can be made flexible while achieving cost reduction, and that can improve weather resistance.
- a further characteristic configuration of the radiative cooling device of the present invention is that the plasticizer is mixed in the range of 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.
- the vinyl chloride resin since the plasticizer mixed in the vinyl chloride resin is mixed in the range of 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, the vinyl chloride resin has appropriate flexibility. can be provided.
- a further characteristic configuration of the radiative cooling device of the present invention is that the aliphatic dibasic acid ester as the plasticizer is an adipate, an adipate copolymer, an azelate, or an azelaate copolymer. , sebacate esters, sebacate ester copolymers, succinate esters and succinate ester copolymers.
- a further characteristic configuration of the radiative cooling device of the present invention is that the aliphatic dibasic acid ester as the plasticizer is an ester bond of an aliphatic dibasic acid and two molecules of a saturated aliphatic alcohol.
- the plasticizer can be properly exposed to ultraviolet rays contained in sunlight. can be made difficult to absorb.
- a further characteristic configuration of the radiative cooling device of the present invention is that the phthalate used as the plasticizer is an ester bond between phthalic acid and two saturated aliphatic alcohol molecules.
- the phthalate ester of the plasticizer is an ester bond of phthalic acid and two molecules of saturated aliphatic alcohol, so that the plasticizer does not easily absorb ultraviolet rays contained in sunlight. can be done.
- a further characteristic configuration of the radiative cooling device of the present invention is that the phosphate ester as the plasticizer is a phosphate triester or an aromatic phosphate ester.
- a phosphate triester or an aromatic phosphate as the phosphate of the plasticizer, it is possible to make the plasticizer less likely to absorb ultraviolet rays contained in sunlight.
- a further characteristic configuration of the radiative cooling device of the present invention is that the film thickness of the resin material layer is The average wavelength of light absorptance at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m is 13% or less, the average wavelength of light absorptance at a wavelength of 0.5 ⁇ m to 0.8 ⁇ m is 4% or less, and the wavelength from 0.8 ⁇ m
- the wavelength average of the light absorption rate up to a wavelength of 1.5 ⁇ m is within 1%
- the wavelength average of the light absorption rate from 1.5 ⁇ m to 2.5 ⁇ m has a light absorption characteristic of 40% or less
- from 8 ⁇ m to The thickness is adjusted to provide thermal radiation characteristics such that the wavelength average of the emissivity of 14 ⁇ m is 40% or more.
- the wavelength average of light absorptance at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m means the average value of light absorptance for each wavelength in the range of 0.4 ⁇ m to 0.5 ⁇ m.
- Other similar descriptions including emissivity mean similar average values, and the same applies hereinafter in this specification.
- the resin material layer changes its light absorption rate and emissivity (light emissivity) depending on its thickness. Therefore, it is necessary to adjust the thickness of the resin material layer so that it absorbs as little sunlight as possible and emits a large amount of thermal radiation in the so-called atmospheric window wavelength range (light wavelength range of 8 ⁇ m to 14 ⁇ m).
- the wavelength average of the light absorption rate at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m is 13% or less, and the wavelength is 0.5 ⁇ m.
- the wavelength average of the light absorptance from the wavelength of 0.8 ⁇ m to the wavelength of 0.8 ⁇ m is 4% or less, the wavelength average of the light absorptance from the wavelength of 0.8 ⁇ m to the wavelength of 1.5 ⁇ m is within 1%, and the wavelength of 1.5 ⁇ m to 2.5 ⁇ m.
- the wavelength average of the light absorptance up to 5 ⁇ m must be 40% or less.
- the wavelength average should be 100% or less.
- the light absorptance of sunlight is 10% or less, which is 100 W or less in terms of energy.
- the light absorption rate of sunlight increases as the film thickness of the resin material layer increases.
- the emissivity of the atmospheric window becomes approximately 1, and the thermal radiation emitted into space at that time is 125 W/m 2 to 160 W/m 2 .
- the absorption of sunlight by the light reflecting layer is preferably 50 W/m 2 or less. Therefore, the sum of sunlight absorption in the resin material layer and the light reflecting layer is 150 W/m 2 or less, and if the atmospheric conditions are favorable, cooling proceeds.
- the average wavelength of the emissivity at wavelengths of 8 ⁇ m to 14 ⁇ m must be 40% or more. That is, in order for the resin material layer to emit into space about 50 W/m 2 of solar thermal radiation absorbed by the light reflecting layer, the resin material layer needs to emit more thermal radiation.
- the maximum thermal radiation of an atmospheric window with a wavelength of 8 ⁇ m to 14 ⁇ m is 200 W/m 2 (calculated as an emissivity of 1). This value can be obtained in fine weather in a very dry environment with thin air, such as in high mountains. Since the atmosphere is thicker in lowlands and the like than in high mountains, the wavelength band of the window of the atmosphere becomes narrower and the transmittance decreases. By the way, this phenomenon is called "the window of the atmosphere becomes narrower".
- the environment in which the radiative cooling device is actually used may be humid, and even in that case the window to the atmosphere is narrow.
- the thermal radiation generated in the atmospheric window region in low-lying applications is estimated to be 160 W/m 2 at 30° C. under good conditions (calculated as an emissivity of 1).
- the window of the atmosphere becomes even narrower and the radiation into space is about 125 W/m 2 .
- the average wavelength of the emissivity of wavelengths 8 ⁇ m to 14 ⁇ m must be 40% or more (the thermal radiation intensity in the window zone of the atmosphere must be 50 W/m 2 or more) to be used in the lowlands of the mid-latitudes. Therefore, by adjusting the thickness of the resin material layer so as to fall within the optically specified range described above, the heat output from the atmospheric window becomes greater than the heat input due to the absorption of sunlight, and the sunlight in the daytime becomes larger. Radiative cooling can be performed outdoors even under environmental conditions.
- the heat output from the atmospheric window is greater than the heat input due to the absorption of sunlight, and radiative cooling can be performed outdoors even in a solar environment.
- a further characteristic configuration of the radiative cooling device of the present invention is that the thickness of the resin material layer is 100 ⁇ m or less and 10 ⁇ m or more.
- the resin material forming the resin material layer is a vinyl chloride-based resin
- the thickness of the resin material layer is 100 ⁇ m or less and 10 ⁇ m or less, appropriate radiative cooling can be performed outdoors even in a solar radiation environment.
- the heat output from the window of the atmosphere is greater than the heat input due to the absorption of sunlight, and appropriate radiative cooling is performed outdoors even in a solar environment. can.
- a further characteristic configuration of the radiative cooling device of the present invention is that the light reflecting layer has a reflectance of 90% or more at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m and a reflectance of 96% or more at a wavelength longer than 0.5 ⁇ m. at the point.
- the sunlight spectrum exists from 0.295 ⁇ m to 4 ⁇ m in wavelength, and the intensity increases as the wavelength increases from 0.4 ⁇ m, especially from 0.5 ⁇ m to 2.5 ⁇ m.
- the light reflective layer exhibits a reflectance of 90% or more at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m and has a reflectance of 96% or more at a wavelength longer than 0.5 ⁇ m, the light reflective layer can reflect sunlight. Absorbs less than 5% of energy.
- the solar energy absorbed by the light reflecting layer can be reduced to about 50 W/m 2 or less during the middle of summer, and radiative cooling by the resin material layer can be performed satisfactorily.
- the spectrum of sunlight is based on the AM1.5G standard.
- the radiative cooling device of the present invention it is possible to suppress the absorption of sunlight energy by the light reflecting layer and to perform radiative cooling by the resin material layer satisfactorily.
- a further characteristic configuration of the radiative cooling device of the present invention is that the light reflecting layer is made of silver or a silver alloy and has a thickness of 50 nm or more.
- the light reflecting layer is provided with the above-mentioned reflection characteristics, that is, the reflectance of 90% or more at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m and the reflectance of 96% or more at a wavelength longer than 0.5 ⁇ m.
- the reflecting material on the emitting surface side of the light reflecting layer must be silver or a silver alloy.
- the thickness when sunlight is reflected in a state in which only silver or a silver alloy has the above-described reflective properties, the thickness must be 50 nm or more.
- the radiative cooling device of the present invention it is possible to appropriately suppress the absorption of solar energy by the light reflecting layer, and to perform the radiative cooling by the resin material layer satisfactorily.
- a further characteristic configuration of the radiative cooling device of the present invention is that the light reflecting layer is a laminate of silver or a silver alloy located on the side where the resin material layer exists and aluminum or an aluminum alloy located on the side away from the resin material layer. It is in the point that it is a structure.
- the light reflecting layer in order to give the light reflecting layer the reflectance characteristics described above, it may have a structure in which silver or a silver alloy and aluminum or an aluminum alloy are laminated.
- the reflecting material on the emitting surface side must be silver or a silver alloy.
- the thickness of silver is required to be 10 nm or more, and the thickness of aluminum is required to be 30 nm or more.
- the light reflecting layer Since aluminum or an aluminum alloy is cheaper than silver or a silver alloy, it is possible to reduce the cost of the light reflecting layer while providing appropriate reflectance characteristics. In other words, while making the expensive silver or silver alloy thinner to reduce the cost of the light reflecting layer, the light reflecting layer has a laminated structure of silver or a silver alloy and aluminum or an aluminum alloy. It is possible to reduce the cost of the light reflecting layer while providing good reflectance characteristics.
- the radiative cooling device of the present invention it is possible to reduce the cost of the light reflecting layer while providing appropriate reflectance characteristics.
- a further characteristic configuration of the radiative cooling device of the present invention is configured to include a protective layer between the infrared radiation layer and the light reflecting layer,
- the protective layer is a polyolefin resin with a thickness of 300 nm or more and 40 ⁇ m or less, or a polyethylene terephthalate resin with a thickness of 17 ⁇ m or more and 40 ⁇ m or less.
- the sunlight incident from the radiation surface of the resin material layer as the infrared radiation layer passes through the resin material layer and the protective layer, and then passes through the light reflecting layer on the side opposite to the radiation surface of the resin material layer. , and escapes from the radiation surface to the outside of the system.
- the protective layer is made of polyolefin resin and has a thickness of 300 nm or more and 40 ⁇ m or less, or is made of ethylene terephthalate resin and has a thickness of 17 ⁇ m or more and 40 ⁇ m or less. Even in a daytime sunlight environment, discoloration of the silver or silver alloy of the light reflection layer can be suppressed. can be performed accurately.
- radicals generated in the resin material layer reach silver or silver alloy forming the light reflecting layer, and moisture passing through the resin material layer forms the light reflecting layer.
- the silver or silver alloy of the light reflecting layer may discolor in a short period of time, resulting in a state in which the light reflecting function is not properly exhibited. Short-term discoloration of silver or silver alloy in the layer can be suppressed.
- the protective layer is made of polyolefin resin and has a thickness of 300 nm or more and 40 ⁇ m or less, the polyolefin resin is exposed to ultraviolet rays in the entire ultraviolet wavelength range of 0.3 ⁇ m to 0.4 ⁇ m. Since the protective layer is a synthetic resin having a light absorption rate of 10% or less, the protective layer is less likely to deteriorate due to the absorption of ultraviolet rays.
- the thickness of the polyolefin-based resin forming the protective layer is 300 nm or more, radicals generated in the resin material layer are blocked from reaching the silver or silver alloy forming the light reflecting layer, and It satisfactorily exhibits a blocking function such as blocking moisture passing through the resin material layer from reaching the silver or silver alloy forming the light reflecting layer, thereby preventing discoloration of the silver or silver alloy forming the light reflecting layer. can be suppressed.
- the protective layer formed of polyolefin resin deteriorates while forming radicals on the surface side away from the reflective layer due to the absorption of ultraviolet rays, but since the thickness is 300 nm or more, the formed radicals does not reach the light-reflecting layer, and even if it deteriorates while forming radicals, the progress of deterioration is slow due to the low absorption of ultraviolet rays. It will be demonstrated.
- the protective layer is made of ethylene terephthalate resin and has a thickness of 17 ⁇ m or more and 40 ⁇ m or less
- the ethylene terephthalate resin has a wavelength range of 0.3 ⁇ m to 0.4 ⁇ m than the polyolefin resin.
- the resin material has a high absorption rate of ultraviolet rays in the wavelength range of ultraviolet rays, since the thickness is 17 ⁇ m or more, the radicals generated in the resin material layer do not reach the silver or silver alloy forming the light reflecting layer.
- the protective layer satisfactorily exhibits a blocking function such as blocking moisture passing through the resin material layer from reaching the silver or silver alloy forming the light reflecting layer for a long period of time. Discoloration of the silver or silver alloy that forms the can be suppressed.
- the protective layer formed of ethylene terephthalate resin deteriorates while forming radicals on the surface side away from the reflective layer due to the absorption of ultraviolet rays. Radicals do not reach the reflective layer, and even if the reflective layer deteriorates while forming radicals, the thickness is 17 ⁇ m or more, so the above shielding function is exhibited over a long period of time.
- the reason for setting the upper limit of the thickness is to avoid as much as possible that the protective layer exhibits heat insulation properties that do not contribute to radiative cooling. .
- the silver or silver alloy of the light reflecting layer can be cooled well while suppressing discoloration in a short period of time.
- a further characteristic configuration of the radiative cooling device of the present invention is that the resin material layer, the protective layer, and the light reflecting layer are laminated to form a film.
- a radiative cooling device in which a resin material layer, a protective layer, and a light reflecting layer are laminated is manufactured as a radiative cooling film. Since the resin material layer and the protective layer are flexible, the light reflecting layer is formed into a thin film, and the light reflecting layer is made flexible. will be prepared.
- the film-like and flexible radiative cooling device can be retrofitted to the outer walls of existing outdoor equipment to provide radiative cooling performance.
- a radiative cooling device in the form of a film.
- a protective layer and a resin material layer may be applied to a film-like light reflecting layer.
- a protective layer and a resin material layer may be attached to a film-like light reflecting layer.
- a protective layer may be formed by coating or adhering on a resin material layer produced in the form of a film, and a light reflecting layer may be produced on the protective layer by vapor deposition, sputtering, ion plating, silver mirror reaction, or the like. Conceivable.
- the radiative cooling device of the present invention it is possible to retrofit existing equipment to give radiative cooling performance.
- a further characteristic configuration of the radiative cooling device of the present invention is that the resin material layer and the protective layer are joined by a joining layer of an adhesive or a pressure-sensitive adhesive.
- the resin material layer and the protective layer are bonded with a bonding layer of an adhesive or pressure-sensitive adhesive, for example, the light reflecting layer and the protective layer are formed in a laminated state, and the resin material layer is prepared separately.
- the resin material layer, the protective layer, and the light reflecting layer can be satisfactorily laminated by the procedure of bonding the protective layer and the protective layer with the bonding layer.
- radicals are also generated from the bonding layer. If the thickness of the ethylene terephthalate resin forming the protective layer is 17 ⁇ m or more, it is possible to prevent radicals generated in the bonding layer from reaching the light reflecting layer over a long period of time.
- a further characteristic configuration of the radiative cooling device of the present invention is that inorganic fillers are mixed in the resin material layer.
- the resin material layer can be provided with a light-scattering structure by mixing inorganic fillers into the resin material layer.
- a light-scattering structure By providing the light scattering structure, glare on the emitting surface can be suppressed when the emitting surface is viewed.
- Silicon dioxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO) and the like can be suitably used as the inorganic material forming the filler.
- SiO 2 silicon dioxide
- TiO 2 titanium oxide
- Al 2 O 3 aluminum oxide
- MgO magnesium oxide
- both the front and back surfaces of the resin material layer become uneven. Since the bonding layer is positioned between the resin material layer and the protective layer, even if the back surface of the resin material layer is uneven, the resin material layer and the protective layer can be appropriately bonded by the bonding layer. can.
- a further characteristic configuration of the radiative cooling device of the present invention is that both the front and back surfaces of the resin material layer are formed in an uneven shape.
- the resin material layer can be provided with a light scattering structure.
- glare on the emitting surface can be suppressed when the emitting surface is viewed.
- the bonding layer is positioned between the resin material layer and the protective layer, even if the back surface of the resin material layer is uneven, the resin material layer and the protective layer can be appropriately bonded by the bonding layer. can.
- FIG. 3 shows the light reflectance spectrum of a silver-based light reflective layer; It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the specific structure of a radiation cooling device. It is a figure which shows the relationship between the light transmittance of polyethylene, and a wavelength. It is a figure explaining the structure for a test.
- FIG. 3 shows the light reflectance spectrum of a silver-based light reflective layer
- FIG. 4 is a diagram showing test results when the protective layer is polyethylene.
- FIG. 10 is a diagram showing test results when the protective layer is UV-absorbing acrylic;
- FIG. 4 shows the emissivity spectrum of polyethylene;
- It is a figure explaining another structure of a radiation cooling device.
- the radiative cooling device CP is located on an infrared radiation layer A that emits infrared light IR from the radiation surface H and on the opposite side of the infrared radiation layer A from the radiation surface H. and a protective layer D between the infrared emitting layer A and the light reflecting layer B are laminated and formed into a film. That is, the radiative cooling device CP is configured as a radiative cooling film.
- the light reflecting layer B reflects light L such as sunlight transmitted through the infrared radiation layer A and the protective layer D.
- the reflectivity is 90% or more at a wavelength of 0.4 ⁇ m to 0.5 ⁇ m, and 96% or more at a wavelength longer than 0.5 ⁇ m.
- the sunlight spectrum exists from a wavelength of 0.295 ⁇ m (295 nm) to 4 ⁇ m (4000 nm), and the intensity increases as the wavelength increases from 0.4 ⁇ m (400 nm), especially from a wavelength of 0.5 ⁇ m (500 nm) to a wavelength of 1.8 ⁇ m. (1800 nm) has a large intensity.
- the light L includes ultraviolet light (ultraviolet light), visible light, and infrared light. .01 ⁇ m to 20 ⁇ m electromagnetic waves).
- the wavelength range of ultraviolet light (ultraviolet rays) is assumed to be 295 nm (0.295 ⁇ m) or more and 400 nm (0.4 ⁇ m) or less.
- the light reflecting layer B exhibits a reflection characteristic of 90% or more in the wavelength range of 0.4 ⁇ m to 0.5 ⁇ m, and exhibits a reflection characteristic of 96% or more in the wavelength longer than 0.5 ⁇ m, whereby the radiative cooling device CP ( The radiation cooling film) can suppress the solar energy absorbed by the light reflecting layer B to 5% or less.
- the light reflecting layer B is composed of silver or a silver alloy, or a laminated structure of silver or a silver alloy located adjacent to the protective layer D and aluminum or an aluminum alloy located on the side away from the protective layer D (in other words, For example, a laminated structure of silver or a silver alloy located on the side where the resin material layer J exists and aluminum or an aluminum alloy located on the side away from the resin material layer J), and has flexibility. , the details of which will be described later.
- the infrared radiation layer A is configured as a resin material layer J having a thickness adjusted to emit thermal radiation energy greater than the absorbed solar energy in a wavelength band of 8 ⁇ m to 14 ⁇ m.
- the resin material forming the resin material layer J is vinyl chloride resin mixed with a plasticizer.
- the resin material forming the resin material layer J may be vinylidene chloride resin mixed with a plasticizer.
- the radiative cooling device CP reflects a part of the light L incident on the radiative cooling device CP by the radiation surface H of the infrared radiation layer A, and the light L incident on the radiative cooling device CP is Light (sunlight, etc.) transmitted through the resin material layer J and the protective layer D is reflected by the light reflecting layer B and escaped from the radiation surface H to the outside.
- heat input to the radiative cooling device CP from the object to be cooled E located on the opposite side of the light reflection layer B from the side on which the resin material layer J is present (for example, heat input by heat conduction from the object to be cooled E). is converted into infrared light IR by the resin material layer J and radiated to cool the object E to be cooled.
- the radiative cooling device CP reflects the light L irradiated to the radiative cooling device CP, and also transfers heat to the radiative cooling device CP (for example, heat transfer from the atmosphere or heat transfer from the object to be cooled E). heat) to the outside as infrared light IR.
- the resin material layer J, the protective layer D, and the light reflecting layer B are flexible, so that the radiation cooling device CP (radiation cooling film) is flexible.
- the radiation cooling device CP will be used to implement a radiation cooling method in which the infrared light IR is emitted from the radiation surface H of the resin material layer J opposite to the surface in contact with the light reflecting layer B.
- a radiative cooling method is implemented in which the radiation surface H faces the sky and infrared light IR is emitted from the radiation surface H facing the sky.
- the resin material (vinyl chloride resin) forming the resin material layer J changes its light absorption rate and emissivity (light emissivity) depending on its thickness. Therefore, it is necessary to adjust the thickness of the resin material layer J so that it absorbs as little sunlight as possible and emits a large amount of thermal radiation in the so-called atmospheric window wavelength band (wavelength band from 8 ⁇ m to 14 ⁇ m).
- the thickness of the resin material layer J is such that the average wavelength of the light absorption rate at wavelengths of 0.4 ⁇ m to 0.5 ⁇ m is 13% or less, and the wavelength is from 0.5 ⁇ m to 13%.
- the wavelength average of light absorption at a wavelength of 0.8 ⁇ m is 4% or less, the wavelength average of light absorption from a wavelength of 0.8 ⁇ m to a wavelength of 1.5 ⁇ m is within 1%, and a wavelength of 1.5 ⁇ m to 2.5 ⁇ m. It is necessary to adjust the thickness so that the wavelength average of light absorptance from 2.5 ⁇ m to 4 ⁇ m is 100% or less.
- the light absorptance of sunlight is 10% or less, which is 100 W or less in terms of energy.
- the light absorption rate of the resin material increases as the film thickness of the resin material increases.
- the emissivity of the atmospheric window becomes approximately 1, and the thermal radiation released into space at that time is 125 W/m 2 to 160 W/m 2 .
- the absorption of sunlight by the protective layer D and the light reflecting layer B is 50 W/m 2 or less.
- the sum of the sunlight absorption in the resin material layer J, the protective layer D, and the light reflecting layer B is 150 W/m 2 or less, and if the atmospheric conditions are good, cooling proceeds.
- the resin material forming the resin material layer J it is preferable to use a resin material having a small light absorptance near the peak value of the sunlight spectrum as described above.
- the thickness of the resin material layer J must be adjusted so that the average wavelength of emissivity at wavelengths from 8 ⁇ m to 14 ⁇ m is 40% or more.
- the thermal energy of the sunlight of about 50 W/m 2 absorbed by the protective layer D and the light reflecting layer B to be emitted from the resin material layer J into space by the thermal radiation of the resin material layer J
- the thermal radiation of more than that is required. must be provided by the resin material layer J.
- the maximum thermal radiation of an 8 ⁇ m to 14 ⁇ m atmospheric window is 200 W/m 2 (calculated as an emissivity of 1).
- This value can be obtained in fine weather in a very dry environment with thin air, such as in high mountains. Since the atmosphere is thicker in lowlands and the like than in high mountains, the wavelength band of the window of the atmosphere becomes narrower and the transmittance decreases. By the way, this phenomenon is called "the window of the atmosphere becomes narrower".
- the environment in which the radiative cooling device CP may be humid, and even in that case the window to the atmosphere is narrow.
- the thermal radiation generated in the atmospheric window region in low-lying applications is estimated to be 160 W/m 2 at 30° C. under good conditions (calculated as an emissivity of 1).
- the window of the atmosphere becomes narrower and the radiation to space is about 125 W/m 2 .
- the average wavelength of the emissivity in the wavelength range of 8 ⁇ m to 14 ⁇ m must be 40% or more (the thermal radiation intensity in the window zone of the atmosphere is 50 W/m 2 ), or it cannot be used in the lowlands of the mid-latitudes.
- the thickness of the resin material layer J is adjusted so as to fall within the range of the optical regulation in view of the above matter, the heat output from the atmospheric window becomes larger than the heat input due to the absorption of sunlight, and the solar radiation environment. Radiative cooling makes it possible to make the temperature lower than the outside air even under the outdoor environment.
- the thickness of the resin material layer J formed of vinyl chloride resin is 100 ⁇ m or less and 10 ⁇ m or more.
- emissivity ( ⁇ ) and light absorption (A) are equal.
- the light absorptance can be obtained from the absorption coefficient ( ⁇ ) by the following formula (1) (hereinafter sometimes referred to as the light absorptance relational expression).
- A 1-exp(- ⁇ t)---(1) where t is the film thickness. That is, by adjusting the film thickness of the resin material layer J, a large amount of thermal radiation can be obtained in a wavelength band with a large absorption coefficient.
- the absorption coefficient in order to suppress the absorption of sunlight, it is preferable to use a material that has no or a small absorption coefficient in the wavelength range of 0.3 ⁇ m to 4 ⁇ m, particularly 0.4 ⁇ m to 2.5 ⁇ m.
- the light absorptance emissivity
- the sunlight spectrum has only wavelengths longer than 0.295 ⁇ m.
- ultraviolet rays is the range of wavelengths shorter than 0.4 ⁇ m
- visible light is the range of wavelengths 0.4 ⁇ m to 0.8 ⁇ m
- the definition of near infrared rays is the range of wavelengths 0.8 ⁇ m to 3 ⁇ m
- the middle infrared rays is defined as a range from 3 ⁇ m to 8 ⁇ m
- far-infrared rays are defined as a range of wavelengths longer than 8 ⁇ m.
- FIG. 2 shows the absorption spectrum of the vinyl chloride resin with a thickness of 100 ⁇ m in the ultraviolet to visible region.
- FIG. 3 shows the emissivity of vinyl chloride resin (PVC), which is a resin having a carbon-chlorine bond, at an atmospheric window.
- PVC vinyl chloride resin
- the absorption coefficient due to the C--Cl stretching vibration appears in a wide band with a half width of 1 ⁇ m or more around the wavelength of 12 ⁇ m.
- an absorption coefficient derived from bending vibration of C—H of alkene contained in the main chain appears around a wavelength of 10 ⁇ m.
- the wavelength average of the emissivity at a thickness of 10 ⁇ m is 43% at wavelengths from 8 ⁇ m to 14 ⁇ m, which falls within the definition of the wavelength average of 40% or more. As shown, as the film thickness increases, the emissivity in the atmospheric window region increases.
- Thermal radiation of the atmospheric window of the resin material layer J occurs near the surface of the resin material. As shown in FIG. 3, in the case of vinyl chloride resin, even if the thickness exceeds 100 ⁇ m, there is almost no increase in heat radiation in the atmospheric window region. That is, in the case of vinyl chloride resin, thermal radiation in the atmospheric window occurs within a depth of about 100 ⁇ m from the surface, and radiation from deeper portions does not come out.
- the thermal radiation in the atmospheric window region generated from the surface of the resin material occurs at a depth of approximately 100 ⁇ m or less from the surface.
- the radiatively cooled cold heat of the radiative cooling device CP is insulated by the resin material that does not contribute to .
- a resin material layer J that ideally does not absorb sunlight at all. In this case, sunlight is absorbed only in the light-reflecting layer B of the radiative cooling device CP.
- the thermal conductivity of resin materials is generally about 0.2 W/m/K, and when calculating considering this thermal conductivity, if the thickness of the resin material layer J exceeds 20 mm, the cooling surface (in the light reflecting layer B The temperature of the surface opposite to the side where the resin material layer J exists) rises.
- the thermal conductivity of resin materials is generally about 0.2 W/m/K.
- the object to be cooled E placed on the side of the light reflecting layer is heated. That is, the thickness of the resin material of the radiative cooling device CP must be 20 mm or less.
- the thickness of the resin material layer J should be thin.
- the thermal conductivity of resin materials is generally lower than that of metals, glass, and the like.
- the film thickness of the resin material layer J should be the minimum necessary. As the film thickness of the resin material layer J increases, the thermal radiation from the atmospheric window increases. When the film thickness exceeds a certain value, the thermal radiation energy from the atmospheric window becomes saturated.
- the saturated film thickness depends on the resin material, but in the case of a resin containing a carbon-chlorine bond, even a thickness of 100 ⁇ m is saturated, and even a thickness of 50 ⁇ m provides sufficient thermal radiation in the window region of the atmosphere. .
- the thinner the resin material the higher the heat transmission coefficient and the more effectively the temperature of the object to be cooled can be lowered. Therefore, the object E to be cooled can be effectively cooled.
- the object to be cooled E can be effectively cooled if the thickness is 100 ⁇ m or less.
- the effect of making it thinner is other than lowering the heat insulation and making it easier to convey cold heat. It is the suppression of light absorption in the near-infrared region derived from CH, CH 2 , and CH 3 in the near-infrared region exhibited by resins containing carbon-chlorine bonds.
- the absorption of sunlight by these can be reduced, so that the cooling capacity of the radiative cooling device CP is increased.
- vinyl chloride resin which is a resin containing carbon-chlorine bonds
- the radiative cooling effect can be more effectively obtained under sunlight when the thickness is 50 ⁇ m or less.
- the reflecting material on the side where the radiation surface H exists (the side where the resin material layer J exists) must be silver or a silver alloy. As shown in FIG. 4, when the light reflecting layer B is composed of silver as a base, the required reflectance of the light reflecting layer B can be obtained.
- the thickness In the case of reflecting sunlight with the reflectance characteristics described above, the thickness must be 50 nm or more only with silver or a silver alloy. However, in order to make the light reflecting layer B flexible, the thickness must be 100 ⁇ m or less. If it is thicker than this, it will be difficult to bend.
- the "silver alloy” is an alloy obtained by adding any of copper, palladium, gold, zinc, tin, magnesium, nickel, and titanium to silver, for example, about 0.4% to 4.5% by mass. can be used. As a specific example, it is possible to use "APC-TR (manufactured by Furuya Metal Co., Ltd.)" which is a silver alloy prepared by adding copper and palladium to silver.
- the reflective material on the side where the radiation surface H exists (the side where the resin material layer J exists) must be silver or a silver alloy.
- the thickness of silver is required to be 10 nm or more, and the thickness of aluminum is required to be 30 nm or more.
- the total thickness of silver and aluminum must be 100 ⁇ m or less. If it is thicker than this, it will be difficult to bend.
- an alloy an alloy in which copper, manganese, silicon, magnesium, zinc, carbon steel for machine structural use, yttrium, lanthanum, gadolinium, and terbium are added to aluminum can be used.
- a protective layer D for protecting silver is required in a form adjacent to silver or a silver alloy. Details of the protective layer D will be described later.
- the plasticizer mixed in the vinyl chloride resin forming the resin material layer J is one or more compounds selected from the group consisting of phthalates, aliphatic dibasic acid esters and phosphate esters.
- a plasticizer is mixed in the range of 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin. From the viewpoint of processing, the weight part of the plasticizer is desirably 100 weight parts or less.
- Aliphatic dibasic acid esters as plasticizers include adipic esters, adipate copolymers, azelaic esters, azelaic ester copolymers, sebacate esters, and sebacate ester copolymers. , succinic acid esters and succinic acid ester copolymers.
- the aliphatic dibasic acid ester as the plasticizer is preferably an aliphatic dibasic acid and two molecules of saturated aliphatic alcohol which are ester-bonded.
- the phthalic acid ester of the plasticizer is preferably formed by ester-bonding phthalic acid and two saturated aliphatic alcohol molecules.
- the phosphate used as the plasticizer is preferably a phosphate triester or an aromatic phosphate.
- DMP dimethyl phthalate
- DEP diethyl phthalate
- DPP dibutyl phthalate
- DOP di-2-ethylhexyl phthalate
- DINP diisononyl phthalate
- DIDP diisodecyl phthalate
- DUP ditridecyl phthalate
- DTDP bis(2-ethylhexyl) terephthalate
- DOIP bis(2-ethylhexyl) isophthalate
- DBA dibutyl adipate
- DIBA diisobutyl adipate
- DOA di-2-ethylhexyl adipate
- DINA diisononyl adipate
- DIDA diisodecyl adipate
- DBS dibutyl sebacate
- DOS di-2-ethylhexyl sebacate
- DINS diethyl succinate
- TMP trimethyl phosphate
- TOP triethyl phosphate
- TBP tributyl phosphate
- TOP tris(2-ethylhexyl) phosphate
- TPP triphenyl phosphate
- TCP tricresyl phosphate
- TXP trixylenyl phosphate
- CDP tresyldiphenyl phosphate
- 2-ethylhexyldiphenyl phosphate 2-ethylhexyldiphenyl phosphate.
- Plasticizers for vinyl chloride resins include phthalates, aliphatic dibasic acid esters, phosphate triesters, aromatic phosphates, trimellitates, and epoxidized fatty acid esters. The following compounds were selected from these plasticizers, mixed with 43 parts by weight of various plasticizers with 100 parts by weight of vinyl chloride, and evaluated by the xenon weather test. In the vinyl chloride resin, 0.5 parts by weight of each of a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer were kneaded with 100 parts by weight of vinyl chloride.
- Typical phthalates include di-2-ethylhexyl phthalate (DOP) and diisodecyl phthalate (DIDP).
- DOP di-2-ethylhexyl phthalate
- DIDP diisodecyl phthalate
- Typical examples of aliphatic dibasic acid esters include di-2-ethylhexyl adipate (DOA), butanediol adipate copolymer (average molecular weight of about 1000), and diisononyl adipate (DINA).
- TBP di-2-ethylhexyl adipate
- DINA diisononyl adipate
- TBP Tributyl phosphate
- TCP Tricresyl phosphate
- a representative trimellitate is tri-2-ethylhexyl trimellitate (TOTM).
- Epoxidized soybean oil is representative of epoxidized fatty acid esters.
- a durability test was carried out for 1,920 hours (corresponding to 4 years of actual exposure) to determine the durability. Incidentally, 487 hours are equivalent to one year in terms of ultraviolet rays.
- the conditions of the xenon weather test are as follows. UV intensity 180 W/m 2 (wavelength 295-400 nm). ⁇ Conditions without watering> BPT 89°C, humidity 50%, 1 hour 42 minutes. ⁇ Conditions with water sprinkling> Temperature in tank 38°C, humidity 90%, 18 minutes.
- phthalates, aliphatic dibasic esters, phosphate triesters, and aromatic phosphate esters lasted for about four years.
- plasticizers mixed in vinyl chloride resin even after about four years, radiation
- the reflectance of the cooling device CP does not decrease, but if a trimellitic acid ester or an epoxidized fatty acid ester is used as a plasticizer mixed with the vinyl chloride resin, the reflectance of the radiative cooling device CP will increase for about 4 years. I've noticed a big drop since then.
- phthalates, aliphatic dibasic acid esters, phosphate triesters, and aromatic phosphate esters have excellent durability as plasticizers for vinyl chloride resins. It can be seen that acid esters and epoxidized fatty acid esters are not durable. The reason for this will be discussed later.
- the vinyl chloride resin forming the resin material layer J may contain flame retardants, stabilizers, stabilizer aids, fillers, antioxidants, ultraviolet absorbers, and light stabilizers.
- Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; Phosphorus compounds, halogen compounds such as chlorinated paraffin, and the like are exemplified. Further, the blending amount of the flame retardant is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
- Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid.
- Metal soap compounds such as zinc, organic tin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate and dibutyltin dilaurate, and antimony mercaptide compounds are exemplified.
- the amount of the stabilizer to be blended is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
- Stabilizing aids include phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite, beta-diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol and the like. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. Further, the amount of the stabilizing aid compounded with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.
- Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders such as glass, carbon, and metals; glass spheres; graphite; aluminum hydroxide; barium sulfate; Examples include magnesium, magnesium carbonate, magnesium silicate, and calcium silicate. Also, the amount of the filler compounded with respect to 100 parts by weight of the vinyl chloride resin is about 1 to 100 parts by weight.
- Antioxidants include 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, 2-hydroxy-4-methoxybenzophenone, and the like.
- the amount of the antioxidant added to 100 parts by weight of the vinyl chloride resin is about 0.2 to 20 parts by weight.
- UV absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; Examples include benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds, and triazine compounds. Further, the blending amount of the ultraviolet absorber is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
- Light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2, 2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl) -4-hydroxyphenyl]methyl]butylmalonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester and 1,1-dimethylethyl hydroperoxide Reaction products of octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, ester mixtures of 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acids, tetrakis(2,2,2,2,6,6-t
- the radiative cooling device CP of the present invention can be of film construction, as shown in FIGS. Since the resin material forming the resin material layer J and the protective layer D is flexible, if the light reflecting layer B is made thin, the light reflecting layer B can also be made flexible.
- the CP can be a flexible film (radiative cooling film).
- the film-like radiative cooling device CP can be retrofitted to existing objects by applying glue and wrapping it to the outer circumference of a car, the outer wall of a warehouse or building, or the outer circumference of a helmet to exert radiative cooling. Then, the radiative cooling ability can be exhibited easily.
- the film-like radiative cooling device CP can be installed on the outer surface of various tents, the outer surface of boxes that store electrical equipment, the outer surface of containers for transporting goods, and the milk tank that stores milk. Anything that needs to be cooled can be targeted, such as the outer surface, the outer surface of the milk reservoir of a milk tank truck.
- the radiative cooling device CP in the form of a film.
- the protective layer D and the resin material layer J are adhered to the light reflecting layer B which is made in the form of a film.
- the protective layer D is coated or attached on the resin material layer J formed in a film form, and a light reflecting layer is formed on the protective layer D by vapor deposition, sputtering, ion plating, silver mirror reaction, or the like. It is conceivable to produce B.
- the radiative cooling device CP (radiative cooling film) shown in FIG.
- a protective layer D is formed on the light reflecting layer B, and a resin material layer J is formed on the protective layer D.
- FIG. A lower protective layer Ds is also formed below the light reflecting layer B. As shown in FIG.
- the light reflecting layer B is composed of an aluminum layer B1 formed of an aluminum foil functioning as aluminum (aluminum alloy) and a silver layer B2 made of silver or a silver alloy.
- a protective layer D is formed on the light reflecting layer B, and a resin material layer J is formed on the protective layer D.
- the radiative cooling device CP radiative cooling film shown in FIG.
- a method of integrally molding can be adopted.
- the resin material layer J is formed into a film
- the protective layer D and the silver layer B2 are sequentially applied on the film-shaped resin material layer J
- the aluminum layer B1 is coated with the silver layer.
- a method of attaching to B2 can be adopted.
- the light reflecting layer B is formed as a single layer of silver or a silver alloy, or is composed of two layers of silver (silver alloy) and aluminum (aluminum alloy).
- a protective layer D is formed on the upper side of the light reflecting layer B, a resin material layer J is formed on the protective layer D, and a film layer F such as PET is formed on the lower side of the light reflecting layer B. It is what I did.
- the protective layer D is sequentially applied and molded integrally, and a separately formed film-like resin material layer J is bonded (bonded) to the protective layer D with a glue layer N (an example of a bonding layer).
- a glue layer N an example of a bonding layer
- adhesives (adhesives) used in the glue layer N include urethane adhesives (adhesives), acrylic adhesives (adhesives), EVA (ethylene vinyl acetate) adhesives (adhesives), and the like. It is desirable to have high transparency to sunlight.
- the light reflecting layer B is composed of an aluminum layer B1 functioning as aluminum (aluminum alloy) and a silver layer B2 made of silver or a silver alloy (alternative silver).
- the aluminum layer B1 is formed on the upper part of the film layer F (corresponding to the base material) formed in the form of a film of PET (ethylene terephthalate resin) or the like, and the protective layer D is formed on the upper side of the silver layer B2.
- a resin material layer J is formed on the upper side of the protective layer D.
- a protective layer D and a silver layer B2 are applied on the film-shaped resin material layer J to integrally form the resin material layer J, the protective layer D and the silver layer B2, and the aluminum layer B1 and the silver layer B2 are glued together.
- a method of adhering in the layer N can be adopted.
- adhesives (adhesives) used in the glue layer N include urethane adhesives (adhesives), acrylic adhesives (adhesives), EVA (ethylene vinyl acetate) adhesives (adhesives), and the like. It is desirable to have high transparency to sunlight.
- the protective layer D is made of polyolefin resin with a thickness of 300 nm or more and 40 ⁇ m or less, or polyethylene terephthalate with a thickness of 17 ⁇ m or more and 40 ⁇ m or less.
- Polyolefin resins include polyethylene and polypropylene.
- FIG. 2 shows the ultraviolet absorption rate of polyethylene, vinylidene chloride resin, ethylene terephthalate resin, and vinyl chloride resin.
- 9 shows the light transmittance of polyethylene, which is suitable as a synthetic resin for forming the protective layer D. As shown in FIG.
- the radiative cooling device CP (radiative cooling film) exhibits a radiative cooling effect not only at night but also in a solar environment, in order to maintain the state in which the light reflecting layer B exhibits the light reflecting function, By protecting the light reflecting layer B with the protective layer D, it is necessary to prevent the silver of the light reflecting layer B from discoloring under the sunlight environment.
- the protective layer D is formed of polyolefin resin in a form having a thickness of 300 nm or more and 40 ⁇ m or less, the polyolefin resin has a wavelength of 0.3 ⁇ m to 0.4 ⁇ m in the entire ultraviolet wavelength range. Since the protective layer D is made of a synthetic resin having an ultraviolet light absorption rate of 10% or less, it is difficult for the protective layer D to deteriorate due to the absorption of ultraviolet rays.
- the thickness of the polyolefin resin forming the protective layer D is 300 nm or more, the radicals generated in the resin material layer J are blocked from reaching the silver or silver alloy forming the light reflecting layer, In addition, the silver or silver alloy forming the light reflecting layer B exhibits a good shielding function such as blocking moisture passing through the resin material layer J from reaching the silver or silver alloy forming the light reflecting layer B. Alternatively, discoloration of the silver alloy can be suppressed.
- the protective layer D formed of polyolefin resin deteriorates while forming radicals on the surface side away from the light reflecting layer B due to the absorption of ultraviolet rays.
- the formed radicals do not reach the light reflecting layer, and even if the layer deteriorates while forming radicals, the progress of deterioration is slow due to the low absorption of ultraviolet rays. It will perform over the long term.
- the protective layer D is made of ethylene terephthalate resin and has a thickness of 17 ⁇ m or more and 40 ⁇ m or less
- the ethylene terephthalate resin has a wavelength of 0.3 ⁇ m to 0.4 ⁇ m, which is higher than that of the polyolefin resin.
- the synthetic resin has a high ultraviolet light absorption rate in the ultraviolet wavelength range of , since the thickness is 17 ⁇ m or more, the radicals generated in the resin material layer J are transferred to the silver or silver alloy forming the light reflecting layer B. It is possible to satisfactorily exhibit a blocking function over a long period of time, such as blocking moisture from reaching the resin material layer J and blocking moisture passing through the resin material layer J from reaching silver or a silver alloy forming the light reflecting layer. As a result, discoloration of silver or silver alloy forming the light reflecting layer B can be suppressed.
- the protective layer formed of ethylene terephthalate resin deteriorates while forming radicals on the surface side away from the light reflecting layer B due to the absorption of ultraviolet rays.
- the formed radicals do not reach the reflective layer, and even if the reflective layer deteriorates while forming radicals, the thickness is 17 ⁇ m or more, so the above shielding function is exhibited over a long period of time.
- the deterioration of ethylene terephthalate resin is caused by the cleavage of the ester bond between ethylene glycol and terephthalic acid by UV rays to form radicals. This deterioration progresses sequentially from the surface of the ethylene terephthalate resin (PET) irradiated with ultraviolet rays.
- ethylene terephthalate resin PET
- the ester bonds of ethylene terephthalate resin (PET) of about 9 nm are cleaved in order from the irradiated surface per day.
- the cleaved surface ethylene terephthalate resin (PET) does not attack the silver (silver alloy) of the light reflecting layer B, but the ethylene terephthalate resin
- the silver (silver alloy) is discolored.
- a thickness of about 3 ⁇ m is required by adding 9 nm/day and 365 days.
- the thickness In order to make the ethylene terephthalate resin (PET) of the protective layer D durable for 3 years or more, the thickness must be 10 ⁇ m or more. A thickness of 17 ⁇ m or more is required for durability of 5 years or more.
- the reason for setting the upper limit of the thickness is to prevent the protective layer D from exhibiting heat insulation that does not contribute to radiative cooling. be.
- the thicker the protective layer D the more the protective layer D exhibits a heat insulating property that does not contribute to radiative cooling.
- the protective layer D becomes thicker, there is no demerit in preventing the silver (silver alloy) of the light reflecting layer B from being colored, but there is a problem in radiative cooling.
- increasing the thickness increases the thermal insulation of the radiative cooling material.
- a resin whose main component is polyethylene, which is excellent as a synthetic resin for forming the protective layer D does not contribute to radiative cooling even if it is formed thick because the emissivity of the window to the atmosphere is low, as shown in FIG.
- increasing the thickness increases the thermal insulation of the radiative cooling material.
- the thickness of the protective layer D formed of polyolefin resin is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
- the protective layer D when the protective layer D is made of an acrylic resin that absorbs ultraviolet rays well, the protective layer D is decomposed by the ultraviolet rays to form radicals, and the silver soon turns yellow and ceases to function as the radiative cooling device CP. (It absorbs sunlight and heats up when exposed to sunlight like other materials).
- the 600h line in the figure is the reflectance spectrum after a xenon weather test (ultraviolet light energy of 60W/m 2 ) was performed for 600h (hours) under the conditions of JIS standard 5600-7-7.
- the 0h line is the reflectance spectrum before the xenon weather test.
- the protective layer D is made of polyethylene having a low ultraviolet light absorption rate
- the reflectance from the near-infrared region to the visible region does not decrease.
- polyethylene resin polyolefin resin
- whose main component is polyethylene hardly absorbs the ultraviolet rays of the sunlight that reaches the ground.
- Silver coloring as layer B does not occur.
- the 600h line in the figure is the reflectance spectrum after a xenon weather test (ultraviolet light energy of 60W/m 2 ) was performed for 600h (hours) under the conditions of JIS standard 5600-7-7.
- the 0h line is the reflectance spectrum before the xenon weather test.
- the fluororesin system can also be used as a material for forming the protective layer D.
- silicone can also be used as a material for forming the protective layer D from the viewpoint of ultraviolet absorption, but it cannot be used as a material for forming the protective layer D because it has extremely poor adhesion to silver (silver alloy).
- the plasticizer mixed in the vinyl chloride resin will be considered below.
- the deterioration of vinyl chloride resins (films) due to sunlight is largely related to the deterioration of plasticizers due to ultraviolet rays.
- Vinyl chloride resins (containing plasticizers) which are usually used outdoors for a long period of time, are protected from ultraviolet rays contained in sunlight by means of coloring and additives. For example, it is often colored in a color such as black and is in a state where it is difficult to be affected by ultraviolet rays.
- the radiative cooling device CP the absorption of sunlight should be minimized to obtain radiative cooling performance. Therefore, it is not possible to add enough additives, dyes and pigments to protect the plasticizer.
- the radiative cooling device CP for example, as shown in FIG. 7, has a glue layer N (bonding layer) and a protective layer D under a resin material layer J formed of vinyl chloride resin, and silver is provided thereunder. There is a light reflecting layer B. Due to the influence of this light reflecting layer B, the resin material layer J is more susceptible to sunlight. That is, the sunlight that has entered the radiative cooling device CP once is reflected by the light reflecting layer B, and thus passes through the resin material layer J twice. In other words, the influence of sunlight on deterioration is about twice as much as usual.
- the silver A radiative cooling device CP comprising a resin material layer J formed on a light reflecting layer B comprising a will be more affected by sunlight.
- Degradation of an ester plasticizer by ultraviolet rays is mainly caused by absorption of ultraviolet energy by the plasticizer.
- Ultraviolet absorption occurs mainly due to electronic transitions exceeding the bond energy of the plasticizer's ester bond.
- Hydrolysis of the plasticizer mixed in the vinyl chloride resin progresses due to the application of activation energy by ultraviolet rays and water molecules.
- the bond of the plasticizer is broken, the broken bond attacks the surrounding vinyl chloride resin, causing dehydrochlorination and the like, resulting in coloration. This also reduces the mechanical strength.
- the radiative cooling device CP absorbs the sunlight, so that it cannot be cooled in the daytime.
- plasticizers trimellitic acid esters, epoxidized fatty acid esters
- Phthalates, aliphatic dibasic acid esters, phosphate triesters, and aromatic phosphates can be used as plasticizers for the radiative cooling device CP.
- the vinyl chloride resin forming the resin material layer J of the radiative cooling device CP used in the experiment is mixed with an ultraviolet absorber, and the reflectance at the beginning of manufacturing of the radiative cooling device CP is 295 nm or more and 350 nm or less. The range is adjusted to be 10% or less (see FIG. 14).
- This UV absorber is present to protect the paste layer N (bonding layer), the protective layer D, and the light reflecting layer B comprising silver under the resin material layer J, and protects the resin material layer J from UV rays. The protective effect is limited.
- the absorbance (A) of the ultraviolet absorber can be expressed by the following formula (2).
- A 1-exp(- ⁇ t)---(2) where ⁇ is the absorption coefficient and t is the film thickness. From this formula, it can be seen that the light is gradually absorbed by the resin material layer J as it moves through the resin material layer J (vinyl chloride layer). In other words, especially on the sunlight incident side of the resin material layer J (vinyl chloride layer), the UV protection effect of the UV absorber cannot be expected. In other words, as a result of the experiment, it was found that when trimellitic acid was used as the plasticizer, the radiative cooling device CP deteriorated as if it were scooped out from the sunlight-irradiated surface (radiating surface H).
- Suitable plasticizers to be mixed in vinyl chloride resins are phthalates, aliphatic dibasic acid esters, phosphate triesters, and aromatic phosphates, as described above.
- the aliphatic dibasic acid ester is preferably an ester bond between an aliphatic dibasic acid and two saturated aliphatic alcohol molecules, and the phthalate ester is an ester bond between phthalic acid and two saturated aliphatic alcohol molecules. It is preferable that the Further, in each of the phthalates, the aliphatic dibasic acid esters, and the phosphate triesters, it is desirable that the hydrocarbon group of the ester is an alkyl group.
- plasticizers are trimellitate esters, epoxidized fatty acid esters, as described above.
- Plasticizers in which the hydrocarbon group of the phthalate, aliphatic dibasic acid ester, or phosphate triester is an unsaturated hydrocarbon group are also not suitable. That is, it is desirable that the hydrocarbon group of the phthalate, aliphatic dibasic acid ester, and phosphate triester is a saturated hydrocarbon group. In other words, if the hydrocarbon group is an unsaturated hydrocarbon group, the unsaturated bond causes coloration, absorbs sunlight well, and lowers the radiative cooling property.
- the unsaturated bonds absorb sunlight and are cleaved, promoting reactions with surrounding oligomers and vinyl chloride, thereby embrittlement and coloration of the resin material layer J of the radiative cooling device CP.
- the difference between suitable and unsuitable plasticizers is due to the ease with which plasticizers absorb ultraviolet light.
- phthalates which are aromatic carboxylic acid esters, are compared with trimellitates.
- An example of a phthalate is DOP (di-2-ethylhexyl phthalate) and an example of a trimellitate is TOTM (tri-2-ethylhexyl trimellitate).
- DOP di-2-ethylhexyl phthalate
- TOTM tri-2-ethylhexyl trimellitate
- Decomposition in the outdoors under UV light is caused by hydrolysis of ester bonds. Ultraviolet light is the activation energy for the reaction.
- the bond energy of the ester bond of trimellitate is weaker than that of phthalic acid. This difference appears in the difference in ultraviolet absorption.
- trimellitic acid ester is a plasticizer that is also used for soft vinyl chloride electric wires exposed to direct sunlight, but it cannot be used for vinyl chloride that forms the resin material layer J of the radiant cooling device CP even for the same outdoor use.
- the vinyl chloride layer is often sufficiently colored to a color such as black and is in a state where it is difficult to be affected by ultraviolet rays, and deterioration due to ultraviolet rays is unlikely to occur.
- Trimellitates include tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), and triisodecyl trimellitate (TIDTM), but none of them are suitable.
- FIG. 16 shows the absorbance of DOP (di-2-ethylhexyl phthalate) and DBP (dibutyl phthalate) as other phthalates, and it can be seen that they have almost no absorption at wavelengths longer than 295 nm.
- the strength of the ester bond largely depends on the type of carboxylic acid, and the UV absorption tends to be the same if the type of carboxylic acid is the same.
- the hydrocarbon group is an alkyl group
- the light absorption at the longest wavelength side of the ultraviolet region of 400 nm or less is due to the bond energy of the ester bond.
- a phthalate ester whose hydrocarbon group is an alkyl group does not have absorption in the ultraviolet region of wavelengths longer than 295 nm in the spectrum of sunlight on the ground, and is not hydrolyzed by the ultraviolet energy of sunlight.
- the ester bond absorbs the ultraviolet energy of sunlight, and the energy promotes hydrolysis.
- Acids and alcohols produced by hydrolysis absorb ultraviolet rays and promote reactions with surrounding oligomers and vinyl chloride, thereby embrittlement and coloration of the resin material layer J of the radiative cooling device CP.
- phthalate esters and trimellitate esters among aromatic carboxylic acid esters used as plasticizers, but phthalate esters can be used as radiative cooling materials, but trimellitate esters cannot be used. .
- DOA di-2-ethylhexyl adipate
- FIG. 17 shows the absorbance of DOA in the ultraviolet region. It can be seen that the absorbance of DOA is even lower than that of the aforementioned DOP (di-2-ethylhexyl phthalate), which had little absorption at wavelengths longer than 295 nm.
- DOP di-2-ethylhexyl phthalate
- FIG. 14 both the phthalate ester and the aliphatic dibasic ester endured for 2000 hours in the xenon weather test, but optically, the DOA has higher durability.
- Phosphate triesters and aromatic phosphate triesters exist as phosphate ester plasticizers.
- Phosphate esters have large binding energy and are not hydrolyzed by UV light with a wavelength longer than 295 nm. Therefore, it is excellent as a plasticizer for the radiative cooling device CP.
- it is set as phosphate ester, it will become flame-retardant.
- Phosphate triesters include trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP) and tris(2-ethylhexyl) phosphate (TOP), as described above.
- TMP trimethyl phosphate
- TEP triethyl phosphate
- TBP tributyl phosphate
- TOP tris(2-ethylhexyl) phosphate
- FIG. 18 shows the absorbance of tributyl phosphate (TBP), and it can be seen that it hardly absorbs ultraviolet light with a wavelength longer than 295 nm.
- Aromatic phosphates include triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), tresyl diphenyl phosphate (CDP), and 2-ethylhexyl diphenyl phosphate, as described above. . Although illustration is omitted, the aromatic phosphate ester hardly absorbs ultraviolet rays having a wavelength longer than 295 nm.
- Epoxidized fatty acid esters include epoxidized soybean oil, epoxidized linseed oil, and the like, but none of them can be used as a plasticizer mixed with the vinyl chloride resin of the radiant cooling device CP.
- an anchor layer G is provided on top of a film layer F (corresponding to a base material), and above the anchor layer G, a light reflection layer B, a protective layer D, an infrared radiation layer A (plasticizer may be provided with a resin material layer J) of vinyl chloride resin mixed with.
- the film layer F (corresponding to the base material) is formed in a film shape with PET (ethylene terephthalate resin) or the like.
- the anchor layer is introduced to strengthen the adhesion between the film layer F and the light reflecting layer B.
- the anchor layer G is preferably composed mainly of acrylic, polyolefin, or urethane mixed with a compound having an isocyanate group or a melamine resin. It is a coating for parts that are not directly exposed to sunlight, and there is no problem even if it is a material that absorbs ultraviolet rays.
- a resin material layer J (vinyl chloride resin mixed with a plasticizer) constituting the infrared radiation layer A is mixed with an inorganic filler V to provide a light scattering structure.
- both the front and back surfaces of the resin material layer J constituting the infrared radiation layer A may be formed in an uneven shape to provide a light scattering structure. With this configuration, glare on the radiation surface H can be suppressed when the radiation surface H is viewed.
- the resin material layer J has flat front and back surfaces, and has a structure in which the filler V is not mixed.
- this glare can be suppressed by providing a light scattering structure.
- the filler V is mixed in the resin material layer J, if the protective layer D and the light reflecting layer B are present, the case of only the resin material layer J mixed with the filler V or the case of only the light reflecting layer B The light reflectance is improved.
- silicon dioxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO) and the like can be suitably used.
- SiO 2 silicon dioxide
- TiO 2 titanium oxide
- Al 2 O 3 aluminum oxide
- MgO magnesium oxide
- both the front and back surfaces of the resin material layer J become uneven. Further, in order to make both the front and back surfaces of the resin material layer J uneven, it is possible to carry out embossing, surface scratching, or the like.
- a glue layer N (bonding layer) is positioned between the resin material layer J and the protective layer D, as in the configuration described with reference to FIG. is desirable. That is, even if the back surface of the resin material layer J is uneven, the adhesive layer N (bonding layer) is positioned between the resin material layer J and the protective layer D, so that the resin material layer J and the protective layer D are separated. can be properly joined.
- Plasma bonding is a mode in which radicals are formed by plasma radiation on the bonding surface of the resin material layer J and the bonding surface of the protective layer D, and bonding is performed by the radicals.
- the back surface of the protective layer D in contact with the light reflecting layer B becomes uneven, which causes the surface of the light reflecting layer B to become uneven. It is necessary to avoid mixing the filler V. That is, if the surface of the light reflecting layer B is deformed into an uneven shape, light reflection cannot be properly performed, and as a result, radiative cooling cannot be properly performed.
- directly forming an Ag layer on the light diffusion layer refers to an infrared radiation layer A (resin material layer J) in which filler V is mixed or embossed unevenness is provided on the Ag layer side which is the light reflection layer B.
- the light reflection layer B is formed by depositing silver (Ag) on the surface of the layer by vapor deposition or the like.
- the “light diffusion layer on the mirror surface Ag” means that the upper surface of the Ag layer that is the light reflection layer B is formed in a mirror surface, and the upper part of the Ag layer, the protective layer D, and the filler V are mixed or embossed. It means that the infrared radiation layer A (resin material layer J) having unevenness of processing is laminated.
- the surface of the light reflection layer B becomes uneven, so that the light reflectance is greatly reduced.
- the surface of the light reflecting layer B is maintained in a specular state, and an appropriate light reflectance is obtained.
- the object to be cooled E is an object that is in close contact with the back surface of the radiative cooling device CP (radiative cooling film). Target can be applied.
- the radiation surface H of the resin material layer J is exposed as it is, but a hard coat covering the radiation surface H may be provided.
- a hard coat there are UV curable acrylic, heat curable acrylic, UV curable silicone, heat curable silicone, organic/inorganic hybrid, and vinyl chloride, any of which may be used.
- An organic antistatic agent may be used as an additive.
- Urethane acrylate is particularly good among UV curable acrylics.
- the thickness of the hard coat (coating film) is 1 to 50 ⁇ m, preferably 2 to 20 ⁇ m.
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Abstract
Description
前記赤外放射層が、吸収した太陽光エネルギーよりも大きな熱輻射エネルギーを波長8μmから波長14μmの帯域で放つ厚みに調整された樹脂材料層である放射冷却装置に関する。
そして、光反射層が太陽光を十分に反射することより、昼間の日射環境下においても冷却対象を冷やすことができる。
尚、光反射層は、赤外放射層を透過した光に加えて、赤外放射層から光反射層の存在側に放射される光を赤外放射層に向けて反射する作用も奏することになるが、以下の説明においては、光反射層を設ける目的が赤外放射層を透過した光(紫外光、可視光、赤外光)を反射することにあるとして説明する。
また、放射冷却装置に柔軟性を備えさせるために、樹脂材料層の軟質化を図ることが望まれる。つまり、光反射層を、例えば銀の薄膜として構成して、柔軟性を備えさせることに併せて、赤外放射層を構成する樹脂材料層が軟質性を備えれば、放射冷却装置が柔軟性を備えるものとなる。そして、柔軟性を備えさせるにあたり、同時に耐候性を向上させることが望まれる。
このように放射冷却装置が柔軟性及び耐候性を備えれば、既設の屋外設備における外壁等に後付けして、放射冷却性能を与えることができるものとなる等、利便性が向上する。
前記赤外放射層が、吸収した太陽光エネルギーよりも大きな熱輻射エネルギーを波長8μmから波長14μmの帯域で放つ厚みに調整された樹脂材料層であるものであって、その特徴構成は、
前記樹脂材料層を形成する樹脂材料が、可塑剤が混入された塩化ビニル系樹脂であり、
前記可塑剤が、フタル酸エステル類、脂肪族二塩基酸エステル類及びリン酸エステル類からなる群より選択される1つ以上の化合物からなる点にある。
本発明で用いられる塩化ビニル系樹脂とは、塩化ビニルあるいは塩化ビニリデンの単独重合体及び塩化ビニルあるいは塩化ビニリデンの共重合体であり、その製造方法は、従来公知の重合方法で行われる。
つまり、塩化ビニル系樹脂は、その熱輻射特性が大気の窓領域において大きな熱輻射が得られるフッ素樹脂やシリコーンゴムと同等であり、これら樹脂よりもかなり安価であるから、直射日光下で周囲温度よりも温度が低下する放射冷却装置を安価に構成するのに有効である。
また、塩化ビニル系樹脂に可塑剤を入れることにより、傷がついても80℃以上に加熱することで変形し表面傷を無くし平滑化することができ、つまりは傷を自己修復することができる。フッ素樹脂やシリコーンゴムにこの特性はない。軟質塩化ビニル系樹脂のこの特性によって綺麗な状態を長期間維持することができる。このことは長期にわたる放射冷却性能の維持につながる。
このように、可塑剤を入れることにより、放射冷却素材の耐久性が向上する。
また、塩化ビニル系樹脂は、難燃性であり且つ生分解され難いものであるから、屋外で長期間使用する放射冷却装置の樹脂材料層を形成する樹脂材料として好適である。
つまり、塩化ビニル系樹脂に混入する可塑剤が紫外線を吸収すると、可塑剤の加水分解が進む結果、塩化ビニル系樹脂が脱塩酸等を生じて着色(茶色)し、しかも、機械強度の低下を生じる虞があるが、可塑剤が太陽光に含まれている紫外線を吸収し難いものとなるため、可塑剤が混入された塩化ビニル系樹脂の耐候性を向上できるのである。
波長0.4μmから0.5μmの光吸収率の波長平均が13%以下であり、波長0.5μmから波長0.8μmの光吸収率の波長平均が4%以下であり、波長0.8μmから波長1.5μmまでの光吸収率の波長平均が1%以内であり、1.5μmから2.5μmまでの光吸収率の波長平均が40%以下となる光吸収特性を備え、且つ、8μmから14μmの輻射率の波長平均が40%以上となる熱輻射特性を備える状態の厚みに調整されている点にある。
このような光吸収率が分布する場合、太陽光の光吸収率は10%以下となり、エネルギーで言うと100W以下となる。
光反射層での太陽光吸収は50W/m2以下であることが好ましい。
したがって、樹脂材料層と光反射層における太陽光吸収の和が150W/m2以下であり、大気の状態がよければ冷却が進む。樹脂材料層は、以上のように太陽光スペクトルのピーク値付近の吸収率が小さなものを用いるのが良い。
すなわち、光反射層で吸収される50W/m2程度の太陽光の熱輻射を樹脂材料層から宇宙に放出させるには、それ以上の熱輻射を樹脂材料層が出す必要がある。
例えば、外気温が30℃のとき、波長8μmから14μmの大気の窓の熱輻射の最大は200W/m2である(輻射率1として計算)。この値が得られるのは、高山など、空気の薄いよく乾燥した環境の快晴時である。低地などでは大気の厚みが高山よりも厚くなるので、大気の窓の波長帯域は狭くなり、透過率は低下する。ちなみに、このことを「大気の窓が狭くなる」と呼ぶ。
また、日本ではよくあることであるが、空に靄があるときや、スモッグが存在する場合、大気の窓はさらに狭くなり、宇宙への放射は125W/m2程度となる。
したがって、樹脂材料層の厚みを、上述した光学的規定の範囲になるように調整することにより、太陽光の光吸収による入熱よりも大気の窓における出熱の方が大きくなり、昼間の日射環境下でも屋外で放射冷却できるようになる。
光反射層が、波長0.4μmから0.5μmにかけて90%以上の反射率を示し、波長0.5μmより長波の反射率が96%以上である反射特性を備えると、光反射層が太陽光エネルギーを5%程度以下しか吸収しなくなる。
尚、本明細書では、太陽光について、断りのない場合、スペクトルはAM1.5Gの規格とする。
そして、銀または銀合金のみで前述の反射特性を持たせた状態で太陽光を反射する場合、厚さが50nm以上必要である。
つまり、高価な銀または銀合金を薄くして、光反射層の低廉化を図るようにしながらも、光反射層を、銀または銀合金とアルミまたはアルミ合金との積層構造にすることにより、適切な反射率特性を持たせながらも、光反射層の低廉化を図ることができる。
前記保護層が、厚さが300nm以上で、40μm以下のポリオレフィン系樹脂、又は、厚さが17μm以上で、40μm以下のポリエチレンテレフタラート樹脂である点にある。
保護層が、ポリオレフィン系樹脂にて厚さが300nm以上で、40μm以下の形態に形成される場合には、ポリオレフィン系樹脂は、波長0.3μmから0.4μmの紫外線の波長域の全域において紫外線の光吸収率が10%以下である合成樹脂であるから、保護層が紫外線の吸収により劣化し難いものとなる。
そして、樹脂材料層及び保護層が柔軟性を備えているから、光反射層を薄膜状にして、光反射層に柔軟性を備えさせることにより、放射冷却装置(放射冷却フィルム)が、柔軟性を備えることになる。
そして、光散乱構成を備えさせることにより、放射面を見たときに、放射面のギラツキを抑制できるものとなる。
尚、樹脂材料層と保護層との間に接合層が位置するから、樹脂材料層の裏面が凹凸状になっていても、樹脂材料層と保護層とを接合層によって適切に接合することができる。
そして、光散乱構成を備えさせることにより、放射面を見たときに、放射面のギラツキを抑制できるものとなる。
ちなみに、樹脂材料層の表裏両面を凹凸状にするには、エンボス加工や表面に傷を付ける加工等を行うことにより行うことができる。
〔放射冷却装置の基本構成〕
図1に示すように、放射冷却装置CPは、放射面Hから赤外光IRを放射する赤外放射層Aと、当該赤外放射層Aにおける放射面Hの存在側とは反対側に位置させる光反射層Bと、赤外放射層Aと光反射層Bとの間の保護層Dとを積層状態に備え、且つ、フィルム状に形成されている。
つまり、放射冷却装置CPが、放射冷却フィルムとして構成されている。
太陽光スペクトルは、波長0.295μm(295nm)から4μm(4000nm)にかけて存在し、波長0.4μm(400nm)から大きくなるにつれ強度が大きくなり、特に波長0.5μm(500nm)から波長1.8μm(1800nm)にかけての強度が大きい。
樹脂材料層Jの詳細は後述するが、本実施形態では、樹脂材料層Jを形成する樹脂材料が、可塑剤が混入された塩化ビニル樹脂である。尚、樹脂材料層Jを形成する樹脂材料としては、可塑剤が混入された塩化ビニリデン樹脂でもよい。
また、樹脂材料層J、保護層D及び光反射層Bが柔軟性を備えることによって、放射冷却装置CP(放射冷却フィルム)が柔軟性を備えるように構成されている。
樹脂材料層Jを形成する樹脂材料(塩化ビニル樹脂)は、厚みによって光吸収率や輻射率(光放射率)が変化する。そのため、太陽光をできるだけ吸収せず、いわゆる大気の窓の波長帯域(波長8μmから波長14μmの帯域)において大きな熱輻射を発するように樹脂材料層Jの厚みを調整する必要がある。
このような吸収率分布の場合、太陽光の光吸収率は10%以下となり、エネルギーで言うと100W以下となる。
保護層D及び光反射層Bで吸収される50W/m2程度の太陽光の熱エネルギーを、樹脂材料層Jの熱輻射より樹脂材料層Jから宇宙に放出させるには、それ以上の熱輻射を樹脂材料層Jが出す必要がある。
例えば、外気温が30℃のとき、8μmから14μmの大気の窓の熱輻射の最大は200W/m2である(輻射率1として計算)。この値が得られるのは、高山など、空気の薄いよく乾燥した環境の快晴時である。低地などでは大気の厚みが高山よりも厚くなるので、大気の窓の波長帯域は狭くなり、透過率は低下する。ちなみに、このことを「大気の窓が狭くなる」と呼ぶ。
かかる事情を鑑みて、波長8μmから14μmの輻射率の波長平均は40%以上(大気の窓帯での熱輻射強度が50W/m2)ないと中緯度帯の低地で用いることができない。
本実施形態においては、塩化ビニル系樹脂にて形成される樹脂材料層Jの厚みが、100μm以下で10μm以上である。
キルヒホッフの法則により、輻射率(ε)と光吸収率(A)は等しい。光吸収率は吸収係数(α)から下記の式(1)(以下、光吸収率関係式と呼ぶことがある)にて求めることができる。
A=1-exp(-αt)---(1)尚、tは膜厚である。
つまり、樹脂材料層Jの膜厚を調整すると、吸収係数の大きな波長帯域で大きな熱輻射が得られる。屋外で放射冷却する場合、大気の窓の波長帯域である波長8μmから14μmにおいて吸収係数の大きな材料を用いるとよい。
また、太陽光の吸収を抑制するために波長0.3μmから4μm、特に0.4μmから2.5μmの範囲で吸収係数を持たない、或いは小さな材料を用いるとよい。吸収係数と吸収率の関係式からわかるように、光吸収率(輻射率)は樹脂材料の膜厚によって変化する。
厚さ100μmの塩化ビニル樹脂の紫外から可視域の吸収率スペクトルを図2に示すが、波長0.38μmよりも短波長側で光吸収が大きくなる。
炭素-塩素結合に関しては、C-Cl伸縮振動による吸収係数が波長12μmを中心に半値幅1μm以上の広帯域に現れる。
また、塩化ビニル樹脂の場合、塩素の電子吸引の影響で、主鎖に含まれるアルケンのC-Hの変角振動に由来する吸収係数が波長10μmあたりに現れる。
これらの影響で、厚さ10μmの輻射率の波長平均は、波長8μmから14μmにおいて43%であり、波長平均40%以上という規定の中に入る。図示の通り、膜厚が厚くなると大気の窓領域における輻射率は増大する。
図3に示す如く、塩化ビニル樹脂の場合は100μmより厚くなっても大気の窓領域における熱輻射の増大は殆どなくなる。つまり、塩化ビニル樹脂の場合、大気の窓における熱輻射は表面から深さ約100μm以内の部分で生じており、より深い部分の輻射は外に出てこない。
理想的に太陽光を全く吸収しない樹脂材料層Jを光反射層Bの上に作製することを考える。この場合、太陽光は放射冷却装置CPの光反射層Bでのみ吸収される。
樹脂材料の熱伝導率はおしなべて0.2W/m/K程度であり、この熱伝導性を考慮して計算すると、樹脂材料層Jの厚みが20mmを超えると、冷却面(光反射層Bにおける樹脂材料層Jの存在側とは反対側の面)の温度が上昇する。
放射冷却装置CPの実用の観点では、樹脂材料層Jの厚みは薄い方がよい。樹脂材料の熱伝導率は、金属やガラスなどよりも一般に低い。冷却対象物Eを効果的に冷却するには、樹脂材料層Jの膜厚は必要最低限であるのがよい。樹脂材料層Jの膜厚を厚くするほどに大気の窓の熱輻射は大きくなり、ある膜厚を超えると大気の窓における熱輻射エネルギーは飽和する。
以上の観点から、炭素-塩素結合を含む樹脂である塩化ビニル系樹脂の場合、50μm以下の厚さにするとより効果的に日照下において放射冷却効果を出すことができる。
光反射層Bに上述の反射率特性を持たせるためには、放射面Hの存在側(樹脂材料層Jの存在側)の反射材料は銀または銀合金である必要がある。
図4に示す通り、銀をベースとして光反射層Bを構成すれば、光反射層Bに求められる反射率が得られる。
但し、光反射層Bに柔軟性を備えさせるためには、厚さを100μm以下にする必要がある。これ以上厚いと曲げにくくなる。
ちなみに、「銀合金」としては、銀に、銅、パラジウム、金、亜鉛、スズ、マグネシウム、ニッケル、チタンのいずれかを、例えば、0.4質量%から4.5質量%程度添加した合金を用いることができる。具体例としては、銀に銅とパラジウムを添加して作成した銀合金である「APC-TR(フルヤ金属製)」を用いることができる。
銀(銀合金)とアルミ(アルミ合金)の2層で構成する場合、銀の厚みは10nm以上必要であり、アルミの厚みは30nm以上必要である。
但し、光反射層Bに柔軟性を備えさせるためには、銀の厚さとアルミの厚さとの合計を100μm以下にする必要がある。これ以上厚いと曲げにくくなる。
保護層Dの詳細は、後述する。
樹脂材料層Jを形成する塩化ビニル樹脂に混入する可塑剤は、フタル酸エステル類、脂肪族二塩基酸エステル類及びリン酸エステル類からなる群より選択される1つ以上の化合物である。
そして、可塑剤が、塩化ビニル樹脂の100重量部に対して、1重量部以上で、200重量部以下の範囲で混入されている。
加工の観点で可塑剤の重量部は100重量部以下が望ましい。
可塑剤のフタル酸エステルが、フタル酸と飽和脂肪族アルコール2分子とがエステル結合したものであるとよい。
可塑剤としてのリン酸エステルが、リン酸トリエステル、又は、芳香族リン酸エステルであるとよい。
フタル酸エステル類を列挙すると、次の通りである。
フタル酸ジメチル(DMP)、フタル酸ジエチル(DEP)、フタル酸ジブチル(DPP)、フタル酸ジ-2-エチルヘキシル(DOP)、フタル酸ジイソノニル(DINP)、フタル酸ジイソデシル(DIDP)、フタル酸ジウンデシル(DUP)、フタル酸ジトリデシル(DTDP)、テレフタル酸ビス(2-エチルヘキシル)(DOTP)、イソフタル酸ビス(2-エチルヘキシル)(DOIP)等。
脂肪族二塩基酸エステル類を列挙すると、次の通りである。
アジピン酸ジブチル(DBA)、アジピン酸ジイソブチル(DIBA)、アジピン酸ジ-2-エチルヘキシル(DOA)、アジピン酸ジイソノニル(DINA)、アジピン酸ジイソデシル(DIDA)、アゼライン酸ビス-2-エチルヘキシル(DOZ)、セバシン酸ジブチル(DBS)、セバシン酸ジ-2-エチルヘキシル(DOS)、セバシン酸ジイソノニル(DINS)、コハク酸ジエチル(DESU)等。
また、アジピン酸等の2塩基酸とジオール(二官能アルコール、あるいはグリコール)との共重合(ポリエステル化)によって合成された分子量400~4000の脂肪族ポリエステル。
リン酸トリエステルを列挙すると、次の通りである。
トリメチルホスフェート(TMP)、トリエチルホスフェート(TEP)、トリブチルホスフェート(TBP)、トリス(2エチルヘキシル)ホスフェート(TOP)。
芳香族リン酸エステルを列挙すると、次の通りである。
トリフェニルホスフェート(TPP)、トリクレシルホスフェート(TCP)、トリキシレニルホスフェート(TXP)、トレジルジフェニルホスフェート(CDP)、2-エチルヘキシルジフェニルホスフェート。
塩化ビニル樹脂用の可塑剤には、フタル酸エステル類、脂肪族二塩基酸エステル類、リン酸トリエステル類、芳香族リン酸エステル類、トリメリット酸エステル類、エポキシ化脂肪酸エステル類がある。これら可塑剤類から下記化合物を選定し、塩化ビニル100重量部に対し各種可塑剤を43重量部混ぜて、キセノンウエザー試験により評価した。
なお、塩化ビニル樹脂には、トリアジン系の紫外線吸収剤とヒンダードアミン系の光安定剤を塩化ビニル100重量部あたりそれぞれ0.5重量部ずつ混錬した。
脂肪族二塩基酸エステルの代表として、アジピン酸ジ-2-エチルヘキシル(DOA)、アジピン酸ブタンジオール共重合体(平均分子量1000程度)、アジピン酸ジイソノニル(DINA)。
リン酸トリエステルの代表として、トリブチルホスフェート(TBP)。
芳香族リン酸エステルの代表として、トリクレシルホスフェート(TCP)。
トリメリット酸エステルの代表として、トリメリット酸トリ-2-エチルヘキシル(TOTM)。
エポキシ化脂肪酸エステルの代表として、エポキシ化大豆油。
キセノンウエザー試験の条件は以下の通りである。
紫外線強度180W/m2(波長295-400nm)。
〈散水なし条件〉BPT89℃、湿度50%、1時間42分。
〈散水あり条件〉槽内温度38℃、湿度90%、18分。
上記実験の結果、トリメリット酸エステル(TOTM)、及び、エポキシ化脂肪酸エステル(エポキシ化大豆油)を可塑剤として用いると耐久性が著しく下がることが明らかとなった。なお、エポキシ化脂肪酸は1120時間で茶変し試験継続できなくなったので同図に載せていない。
尚、この理由については、後述の如く考察する。
樹脂材料層Jを形成する塩化ビニル樹脂に、難燃剤、安定剤、安定化助剤、充てん剤、酸化防止剤、紫外線吸収剤、光安定剤が入っていてもよい。
<難燃剤>
難燃剤としては、水酸化アルミニウム、三酸化アンチモン、水酸化マグネシウム、ホウ酸亜鉛等の無機系化合物、クレジルジフェニルホスフェート、トリスクロロエチルフォスフェート、トリスクロロプロピルフォスフェート、トリスジクロロプロピルフォスフェート等のリン系化合物、塩素化パラフィン等のハロゲン系化合物等が例示される。又、塩化ビニル樹脂100重量部に対する難燃剤の配合量は0.1~20重量部程度である。
安定剤としては、ステアリン酸リチウム、ステアリン酸マグネシウム、ラウリン酸マグネシウム、リシノール酸カルシウム、ステアリン酸カルシウム、ラウリン酸バリウム、リシノール酸バリウム、ステアリン酸バリウム、オクチル酸亜鉛、ラウリン酸亜鉛、リシノール酸亜鉛、ステアリン酸亜鉛等の金属石鹸化合物、ジメチルスズビス-2-エチルヘキシルチオグリコレート、ジブチルスズマレエート、ジブチルスズビスブチルマレエート、ジブチルスズジラウレート等の有機錫系化合物、アンチモンメルカプタイド化合物等が例示される。又、塩化ビニル樹脂100重量部に対する安定剤の配合量は0.1~20重量部程度である。
安定化助剤としは、トリフェニルホスファイト、モノオクチルジフェニルホスファイト、トリデシルフォスファイト等のホスファイト系化合物、アセチルアセトン、ベンゾイルアセトン等のベータジケトン化合物、グリセリン、ソルビトール、ペンタエリスリトール、ポリエチレングリコール等のポリオール化合物、過塩素酸バリウム塩、過塩素酸ナトリウム塩等の過塩素酸塩化合物、ハイドロタルサイト化合物、ゼオライトなどが例示される。又、塩化ビニル樹脂100重量部に対する安定化助剤の配合量は0.1~20重量部程度である。
充填剤としては、炭酸カルシウム、シリカ、アルミナ、クレー、タルク、珪藻土、フェライト、などの金属酸化物、ガラス、炭素、金属などの繊維及び粉末、ガラス球、グラファイト、水酸化アルミニウム、硫酸バリウム、酸化マグネシウム、炭酸マグネシウム、珪酸マグネシウム、珪酸カルシウムなどが例示される。又、塩化ビニル樹脂100重量部に対する充填剤の配合量は1~100重量部程度である。
酸化防止剤としては、2,6-ジ-tert-ブチルフェノール、テトラキス[メチレン-3-(3,5-tert-ブチル-4-ヒドロキシフェノール)プロピオネート]メタン、2-ヒドロキシ-4-メトキシベンゾフェノンなどのフェノール系化合物、アルキルジスルフィド、チオジプロピオン酸エステル、ベンゾチアゾールなどの硫黄系化合物、トリスノニルフェニルホスファイト、ジフェニルイソデシルホスファイト、トリフェニルホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイトなどのリン酸系化合物、ジアルキルジチオリン酸亜鉛、ジアリールジチオリン酸亜鉛などの有機金属系化合物などが例示される。又、塩化ビニル樹脂100重量部に対する酸化防止剤の配合量は0.2~20重量部程度である。
紫外線吸収剤としては、フェニルサリシレート、p-tert-ブチルフェニルサリシレートなどのサリシレート系化合物、2-ヒドロキシ-4-n-オクトキシベンゾフェノン、2-ヒドロキシ-4-n-メトキシベンゾフェノンなどのベンゾフェノン系化合物、5-メチル-1H-ベンゾトリアゾール、1-ジオクチルアミノメチルベンゾトリアゾールなどのベンゾトリアゾール系化合物の他、シアノアクリレート系化合物、トリアジン系化合物などが例示される。又、塩化ビニル樹脂100重量部に対する紫外線吸収剤の配合量は0.1~10重量部程度である。
光安定剤としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート及びメチル1,2,2,6,6-ペンタメチル-4-ピペリジルセバケート(混合物)、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドリキシフェニル]メチル]ブチルマロネート、デカン二酸ビス(2,2,6,6-テトラメチル-1(オクチルオキシ)-4-ピペリジル)エステル及び1,1-ジメチルエチルヒドロペルオキシドとオクタンの反応生成物、4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン、2,2,6,6-テトラメチル-4-ピペリジノールと高級脂肪酸のエステル混合物、テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシレート、テトラキス(1,2,2,6,6-ペンタメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシレート、コハク酸ジメチルと4-ヒドロキシ-2,2,6,6-テトラメチル-1-ピペリジンエタノールの重縮合物、ポリ[{(6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル){(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}}、ジブチルアミン・1,3,5-トリアジン・N,N'-ビス(2,2,6,6-テトラメチル-4-ピペリジル-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物、N,N',N'',N'''-テトラキス-(4,6-ビス-(ブチル-(N-メチル-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ)-トリアジン-2-イル)-4,7-ジアザデカン-1,10-ジアミン等のヒンダードアミン系が例示される。又、塩化ビニル系樹脂100重量部に対する光安定剤の配合量は0.1~10重量部程度である。
本発明の放射冷却装置CPは、図5から図8に示すように、フィルム構造にすることができる。樹脂材料層J及び保護層Dを形成する樹脂材料は柔軟であるために、光反射層Bを薄膜にすると、光反射層Bにも柔軟性を備えさせることができ、その結果、放射冷却装置CPを、柔軟性を備えるフィルム(放射冷却フィルム)とすることができる。
フィルム状の放射冷却装置CP(放射冷却フィルム)を装着する対象としては、各種のテント類の外面、電気機器等を収納するボックスの外面、物品搬送用コンテナの外面、牛乳を貯留する牛乳タンクの外面、牛乳タンクローリーの牛乳貯留部の外面等、冷却が必要な諸々のものを対象とすることができる。
尚、別の作成方法として、樹脂材料層Jをフィルム状に形成して、当該フィルム状の樹脂材料層Jの上に、保護層D、銀層B2を順次塗布し、アルミ層B1を銀層B2に貼り付ける方法を採用することができる。
のり層Nにて使用する接着剤(粘着剤)は、例えば、ウレタン系接着剤(粘着剤)、アクリル系接着剤(粘着剤)、EVA(エチレン酢酸ビニル)系接着剤(粘着剤)等があり、太陽光に対して高い透明性を持つものが望ましい。
のり層Nにて使用する接着剤(粘着剤)は、例えば、ウレタン系接着剤(粘着剤)、アクリル系接着剤(粘着剤)、EVA(エチレン酢酸ビニル)系接着剤(粘着剤)等があり、太陽光に対して高い透明性を持つものが望ましい。
保護層Dは、厚さが300nm以上で、40μm以下のポリオレフィン系樹脂、又は、厚さが17μm以上で、40μm以下のポリエチレンテレフタラートである。
ポリオレフィン系樹脂としては、ポリエチレン及びポリプロピレンがある。
また、図9に、保護層Dを形成する合成樹脂として好適なポリエチレンの光透過率を示す。
例えば、保護層Dを形成する合成樹脂として優れている主成分がポリエチレンの樹脂は、図13に示すように、大気の窓における輻射率が小さいため、厚く形成しても放射冷却に寄与しない。それどころか、厚くすると放射冷却材料の断熱性を上げることになる。次に、厚くなると主鎖の振動に由来する近赤外域の吸収が増加し、太陽光吸収が増える効果が増加する。
これら要因により、保護層Dが厚いことは、放射冷却にとって不利である。このような観点から、ポリオレフィン系樹脂にて形成される保護層Dの厚さは、5μm以下であることが好ましく、さらには、1μm以下であることが一層好ましい。
保護層Dによる銀の着色のされ方の違いを検討するために、図10に示すような、赤外放射層Aとしての樹脂材料層Jを備えない保護層Dを露出させたサンプルを作製し、模擬太陽光が照射された後の銀の着色を調べた。
つまり、保護層Dとして、紫外線を吸収する一般的なアクリル系樹脂(例えば、ベンゾトリアゾール系紫外線吸収剤が混入するメタクリル酸メチル樹脂)とポリエチレンとの二種類を、バーコーターで、光反射層Bとして銀を備えるフィルム層F(基材に相当)上に塗布したサンプルを形成し、保護層Dとしての機能を検討した。塗布した保護層Dの厚みは、それぞれ10μmと1μmである。
尚、フィルム層F(基材に相当)は、PET(エチレンテレフタラート樹脂)等にてフィルム状に形成されたものである。
尚、図中の600hの線は、JIS規格5600-7-7の条件でキセノンウエザー試験(紫外光エネルギーは60W/m2)を600h(時間)行った後の反射率スペクトルである。また、0hの線は、キセノンウエザー試験を行う前の反射率スペクトルである。
尚、図中の600hの線は、JIS規格5600-7-7の条件でキセノンウエザー試験(紫外光エネルギーは60W/m2)を600h(時間)行った後の反射率スペクトルである。また、0hの線は、キセノンウエザー試験を行う前の反射率スペクトルである。
また、シリコーンも紫外線吸収の観点からは保護層Dを形成する材料に適用できるが、銀(銀合金)との密着性が極めて悪く、保護層Dを形成する材料としては用いることができない。
以下、塩化ビニル系樹脂に混入する可塑剤について考察する。
(塩化ビニル系樹脂の劣化について)
塩化ビニル系樹脂(フィルム)の太陽光による劣化は、可塑剤の紫外線による劣化が大きく関与している。
通常屋外で長期使用される塩化ビニル系樹脂(可塑剤が混入されている)は、着色や添加剤によって太陽光に含まれる紫外線から守られている。例えば黒等の色に着色され、紫外線の影響を受けづらい状態となっていることが多い。一方、放射冷却装置CPの場合、放射冷却性能を得るために太陽光の吸収を最小限に抑える必要がある。そのため可塑剤を守るための添加物や染料・顔料を十分に入れることができない。
これらのことは、銀を備えた光反射層Bの上に樹脂材料層Jを備える放射冷却装置CPの塩化ビニル樹脂は、一般用途の塩化ビニルよりも太陽光に含まれる紫外線に敏感であることを示唆している。
紫外線吸収は、主に可塑剤のエステル結合の結合エネルギーを超える電子遷移が生じることによって生じる。紫外線による活性エネルギーの付与と水分子により、塩化ビニル系樹脂に混入された可塑剤の加水分解が進む。
可塑剤の結合が切れると、切れた結合が周囲の塩化ビニル系樹脂を攻撃し、脱塩酸等生じて着色する。また、このことにより機械強度も低下する。
塩化ビニル系樹脂が着色すると、太陽光を放射冷却装置CPが吸収するために日中では冷却できなくなる。
実験に用いた放射冷却装置CPの樹脂材料層Jを形成する塩化ビニル樹脂には、紫外線吸収剤を混ぜており、放射冷却装置CPの製作当初の反射率が、波長295nm以上で、350nm以下の範囲で10%以下となるよう調整している(図14参照)。
この紫外線吸収剤は、樹脂材料層Jの下にあるのり層N(接合層)、保護層D、銀を備えた光反射層Bを守るために存在しており、樹脂材料層Jを紫外線から守る効果は限定的である。
A=1-exp(-αt)---(2)尚、αは吸収係数、tは膜厚である。
この式から、光は、樹脂材料層J(塩化ビニル層)を移動するに伴って徐々に樹脂材料層Jに吸収されることがわかる。つまり、特に、樹脂材料層J(塩化ビニル層)の太陽光入射側は、紫外線吸収剤による紫外線保護効果は期待できない。
つまり、実験の結果、可塑剤をトリメリット酸とした場合には、放射冷却装置CPが、太陽光照射面(放射面H)からえぐれるようにして劣化が進むことが分かった。
塩化ビニル系樹脂に混入する好適な可塑剤は、上述の如く、フタル酸エステル、脂肪族二塩基酸エステル、リン酸トリエステル、芳香族リン酸エステルである。
脂肪族二塩基酸エステルは、脂肪族二塩基酸と飽和脂肪族アルコール2分子とがエステル結合したものであことが好ましく、フタル酸エステルは、フタル酸と飽和脂肪族アルコール2分子とがエステル結合したものであることが好ましい。
また、フタル酸エステル、脂肪族二塩基酸エステル、リン酸トリエステルの夫々については、エステルの炭化水素基がアルキル基であることが望ましい。
また、フタル酸エステル、脂肪族二塩基酸エステル、リン酸トリエステルの炭化水素基が、不飽和炭化水素基である可塑剤も不適である。つまり、フタル酸エステル、脂肪族二塩基酸エステル、リン酸トリエステルの炭化水素基が、飽和炭化水素基であることが望ましい。
つまり、炭化水素基が不飽和炭化水素基であると、その不飽和結合が着色の原因となり太陽光をよく吸収し、放射冷却特性を下げる。併せて、その不飽和結合が太陽光を吸収して開裂し、周辺のオリゴマー及び塩化ビニルとの反応を進め、このことにより、放射冷却装置CPの樹脂材料層Jが脆化、着色する。
要するに、可塑剤の適・不適の違いは、可塑剤の紫外線の吸収し易さに起因する。
先ずは、芳香族カルボン酸エステルである、フタル酸エステルについて、トリメリット酸エステルと比較する。フタル酸エステルの例としては、DOP(フタル酸ジ-2-エチルヘキシル)があり、トリメリット酸エステルの例としては、TOTM(トリメリット酸トリ-2-エチルヘキシル)がある。
紫外線が照射される屋外での分解はエステル結合の加水分解によって生じる。紫外線がその反応の活性化エネルギーとなる。トリメリット酸エステルのエステル結合の結合エネルギーはフタル酸と比較して弱い。この違いは紫外線吸収の違いに現れる。
λA=1240/E---(3)
この式は、結合エネルギー(E)が小さくなると、結合の電子移動を活性化する紫外線吸収波長が長波にシフトすることを示している。図15にその一例を示す。
図15の中で、DEHP、DINCHがフタル酸エステル、TOTMがトリメリット酸エステルである。尚、DEHPは、DOPと同じである。
ちなみに、トリメリット酸エステルは直射日光に晒される軟質塩ビ製電線等にも用いられる可塑剤であるが、同じ屋外用途でも放射冷却装置CPの樹脂材料層Jを形成する塩化ビニルに用いることはできない。一般的な屋外用途において、塩化ビニル層は黒等の色に十分に着色され、紫外線の影響を受けづらい状態となっていることが多く、紫外線による劣化は生じにくい。
トリメリット酸エステル類としては、トリメリット酸トリ-2-エチルヘキシル(TOTM)、トリメリット酸トリイソノニル(TINTM)、トリメリット酸トリイソデシル(TIDTM)等があるが、いずれも不適である。
炭化水素基がアルキル基のフタル酸エステルは、地上の太陽光スペクトルに存在する295nmよりも長波の紫外域に吸収を有しておらず、太陽光の紫外エネルギーで加水分解が進まない。
つまり、可塑剤として用いられる芳香族カルボン酸エステルには、フタル酸エステルとトリメリット酸エステルが存在するが、フタル酸エステルは放射冷却素材として用いることができるがトリメリット酸エステルは用いることができない。
炭化水素基がアルキル基の場合、エステル結合の強度はカルボン酸の種類に大きく依存しており、カルボン酸の種類が同一であれば紫外線吸収は同様の傾向を示すことはフタル酸とトリメリット酸の部分で説明した。
脂肪族二塩基酸エステルの脂肪族二塩基酸がアジピン酸、アゼライン酸、セバシン酸、コハク酸のように飽和ジカルボン酸であり、なおかつエステルがこれら酸と飽和グルコースとのエステル結合の場合を考える。なお飽和ジカルボン酸と飽和グルコースとの共重合体も含む。
この場合、紫外域において光学的に特徴のある官能基はエステル結合のみとなり、理論上、紫外域(200nm以上で400nm以下)の吸収スペクトルはいずれの脂肪族二塩基酸エステルも同一となる。
図14において、フタル酸エステルも脂肪族二塩基酸エステルもキセノンウエザー試験で2000時間を耐久しているが、光学的には、DOAの方が耐久性は高い。
リン酸エステルの可塑剤には、リン酸トリエステルと芳香族リン酸トリエステルが存在する。リン酸エステルの結合エネルギーは大きく、295nmより長波の紫外線で加水分解しない。故に、放射冷却装置CPの可塑剤として優れている。なお、リン酸エステルとすると、難燃性となる。
図18に、トリブチルホスフェート(TBP)の吸光度を示すが、295nmより長波の紫外線を殆ど吸収しないことがわかる。
図示は省略するが、芳香族リン酸エステルは、295nmより長波の紫外線を殆ど吸収しない。
エポキシ化脂肪酸エステルは、上述したTOTM(トリメリット酸エステル)と同様に、295nmより長波の紫外線をよく吸収する。
つまり、エポキシ化脂肪酸エステルのエポキシ基は、295nmよりも長波の紫外線を吸収し分解する。微生物によっても分解する。そのため、屋外使用する観点で使えない。
尚、エポキシ化脂肪酸エステル類としては、エポキシ化大豆油、エポキシ化亜麻仁油等のエポキシ化エステル類があるが、いずれも放射冷却装置CPの塩化ビニル系樹脂に混入する可塑剤としては使えない。
図19に示すように、フィルム層F(基材に相当)の上部にアンカー層Gを備え、当該アンカー層Gの上部に、光反射層B、保護層D、赤外放射層A(可塑剤が混入された塩化ビニル樹脂の樹脂材料層J)を備える形態に構成してもよい。
尚、フィルム層F(基材に相当)は、例えば、PET(エチレンテレフタラート樹脂)等にてフィルム状に形成されたものである。
尚、フィルム層Fと光反射層Bとの密着を強める方法には、アンカー層Gを入れる以外の方法もある。例えば、フィルム層Fの製膜面にプラズマ照射して表面を荒らすと密着性は高まる。
図20に示すように、赤外放射層Aを構成する樹脂材料層J(可塑剤が混入された塩化ビニル樹脂)に、無機材料のフィラーVを混入させて、光散乱構成を備えさせるようにしてもよい。また、図21に示すように、赤外放射層Aを構成する樹脂材料層Jの表裏両面を凹凸状に形成して、光散乱構成を備えさせるようにしてもよい。
このように構成すれば、放射面Hを見たときに、放射面Hのギラツキを抑制できるものとなる。
また、樹脂材料層JにフィラーVを混入させた場合において、保護層D及び光反射層Bが存在すると、にフィラーVを混入させた樹脂材料層Jのみの場合や光反射層Bのみの場合よりも、光反射率が向上する。
また、樹脂材料層Jの表裏両面を凹凸状にするには、エンボス加工や表面に傷を付ける加工等を行うことにより行うことができる。
つまり、樹脂材料層Jの裏面が凹凸状であっても、樹脂材料層Jと保護層Dとの間にのり層N(接合層)が位置するから、樹脂材料層Jと保護層Dとを適切に接合することができる。
図22における「光拡散層にAg層を直接形成」とは、フィラーVを混入させる或いは光反射層BであるAg層側にエンボス加工の凹凸がある赤外放射層A(樹脂材料層J)の表面に、銀(Ag)を蒸着等により成膜して光反射層Bを形成することを、意味するものである。
また、「鏡面Ag上に光拡散層」とは、光反射層BであるAg層の上面が鏡面状に形成され、当該Ag層の上部、保護層D、及び、フィラーVを混入させる或いはエンボス加工の凹凸がある赤外放射層A(樹脂材料層J)が積層されていることを、意味するものである。
以下、別実施形態を列記する。
(1)上記実施形態では、冷却対象物Eとして、放射冷却装置CP(放射冷却フィルム)の裏面に密着される物体を例示したが、冷却対象物Eとしては、冷却対象空間等、各種の冷却対象を適用できる。
ハードコートとしては、UV硬化アクリル系、熱硬化アクリル系、UV硬化シリコーン系、熱硬化シリコーン系、有機無機ハイブリッド系、塩化ビニルが存在し、いずれを用いてもよい。添加材として有機系帯電防止剤を用いてもよい。
UV硬化アクリル系の中でもウレタンアクリレートは特によい。
ハードコート(塗膜)の厚みは1~50μmであり、特に2~20μmが望ましい。
B 光反射層
D 保護層
H 放射面
J 樹脂材料層
N 接合層
Claims (16)
- 放射面から赤外光を放射する赤外放射層と、当該赤外放射層における前記放射面の存在側とは反対側に位置させる光反射層とを備える形態に構成され、
前記赤外放射層が、吸収した太陽光エネルギーよりも大きな熱輻射エネルギーを波長8μmから波長14μmの帯域で放つ厚みに調整された樹脂材料層である放射冷却装置であって、
前記樹脂材料層を形成する樹脂材料が、可塑剤が混入された塩化ビニル系樹脂であり、
前記可塑剤が、フタル酸エステル類、脂肪族二塩基酸エステル類及びリン酸エステル類からなる群より選択される1つ以上の化合物からなる放射冷却装置。 - 前記可塑剤が、前記塩化ビニル系樹脂の100重量部に対して、1重量部以上、200重量部以下の範囲で混入されている請求項1に記載の放射冷却装置。
- 前記可塑剤としての脂肪族二塩基酸エステルが、アジピン酸エステル類、アジピン酸エステル共重合体類、アゼライン酸エステル類、アゼライン酸エステル共重合体類、セバシン酸エステル類、セバシン酸エステル共重合体類、コハク酸エステル類及びコハク酸エステル共重合体類からなる群より選択される1つ以上の化合物からなる請求項1又は2に記載の放射冷却装置。
- 前記可塑剤としての脂肪族二塩基酸エステルが、脂肪族二塩基酸と飽和脂肪族アルコール2分子とがエステル結合したものである請求項1又は2に記載の放射冷却装置。
- 前記可塑剤としてのフタル酸エステルが、フタル酸と飽和脂肪族アルコール2分子とがエステル結合したものである請求項1又は2に記載の放射冷却装置。
- 前記可塑剤としてのリン酸エステルが、リン酸トリエステル、又は、芳香族リン酸エステルである請求項1又は2に記載の放射冷却装置。
- 前記樹脂材料層の膜厚が、
波長0.4μmから0.5μmの光吸収率の波長平均が13%以下であり、波長0.5μmから波長0.8μmの光吸収率の波長平均が4%以下であり、波長0.8μmから波長1.5μmまでの光吸収率の波長平均が1%以内であり、1.5μmから2.5μmまでの光吸収率の波長平均が40%以下となる光吸収特性を備え、且つ、8μmから14μmの輻射率の波長平均が40%以上となる熱輻射特性を備える状態の厚みに調整されている請求項1~6のいずれか1項に記載の放射冷却装置。 - 前記樹脂材料層の厚みが、100μm以下で10μm以上である請求項1~7のいずれか1項に記載の放射冷却装置。
- 前記光反射層は、波長0.4μmから0.5μmの反射率が90%以上、波長0.5μmより長波の反射率が96%以上である請求項1~8のいずれか1項に記載の放射冷却装置。
- 前記光反射層が、銀または銀合金で構成され、その厚みが50nm以上である請求項1~9のいずれか1項に記載の放射冷却装置。
- 前記光反射層が、前記樹脂材料層の存在側に位置する銀または銀合金と前記樹脂材料層から離れる側に位置するアルミまたはアルミ合金の積層構造である請求項1~9のいずれか1項に記載の放射冷却装置。
- 前記赤外放射層と前記光反射層との間に保護層を備える形態に構成され、
前記保護層が、厚さが300nm以上で、40μm以下のポリオレフィン系樹脂、又は、厚さが17μm以上で、40μm以下のポリエチレンテレフタラート樹脂である請求項10又は11に記載の放射冷却装置。 - 前記樹脂材料層と前記保護層と前記光反射層とが積層された状態においてフィルム状である請求項12に記載の放射冷却装置。
- 前記樹脂材料層と前記保護層とが、接着剤又は粘着剤の接合層にて接合されている請求項12又は13に記載の放射冷却装置。
- 前記樹脂材料層に、無機材料のフィラーが混入されている請求項14に記載の放射冷却装置。
- 前記樹脂材料層の表裏両面が凹凸状に形成されている請求項14に記載の放射冷却装置。
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WO2020195743A1 (ja) * | 2019-03-27 | 2020-10-01 | 大阪瓦斯株式会社 | 放射冷却装置及び放射冷却方法 |
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