JP2012051113A - Heat controllable sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat controllable sheet that has superior heat shielding properties in summer, prevents excessive rise of temperature of sheet, has temperature storage properties in winter, and has a degree of freedom of lighting property and coloring.SOLUTION: The heat controllable sheet is a flexible sheet containing near infrared rays shielding layer, and is obtained by the near infrared ray shielding layer being non-compatible resin layer formed of sea-island dispersed structure comprising mixture of synthetic resin containing metal-insulator transition substance particle, and synthetic resin containing near infrared rays scattering coloring agent.

Description

  The present invention relates to a sheet having thermal controllability. More specifically, the present invention provides heat energy as far-infrared rays under the hot sun in summer to prevent excessive temperature rise of the sheet and shields near-infrared rays contained in sunlight. Suppresses the temperature rise inside the constructed membrane structure, and at low temperatures in winter, it emits less heat from the seats heated by sunlight and heating, etc., and has a heat storage property, especially in tent warehouses and large tents for events The present invention relates to a thermally controllable sheet that can be suitably used for agricultural and horticultural houses, awning tents, awning monuments, decorative tents, blinds, seat shutters, partitions, truck hoods, and the like.

  Light transmissive or semi-transparent sheet with flexible resin coated fiber base fabric, tent warehouse, event tent, agricultural / horticultural house, awning tent, awning monument, decorative tent, blind, sheet shutter It is widely used for outdoor applications related to daily life, such as partitions and truck hoods. However, since these sheets have a low ability to shield near infrared rays contained in sunlight, the internal temperature of the tent warehouse is extremely high in the summer, and the working environment is severe. An awning tent is effective in preventing glare and reducing ultraviolet rays, but has a poor cooling effect. Recently, materials for outdoor facilities that are a combination of thin flexible solar cells and flexible membrane materials have attracted attention. In this application, the sheet and solar cell elements tend to become hot due to solar radiation in the summer, generating power efficiency. And there was a problem affecting practicality.

  In such a sheet, by using a white sheet containing an inorganic white pigment such as titanium oxide, it is possible to scatter near-infrared rays contained in sunlight and prevent its transmission, and to suppress an increase in temperature of the sheet itself. Are known. However, in order to obtain a sufficient temperature rise suppressing effect, it is necessary to use a large amount of white pigment. For this reason, the internal environment of the structure using such a sheet becomes dark, and illumination is necessary even during the day.

  On the other hand, the inventor of the present invention has a light shielding property using a refractive index of 1.8 or more, a particle size distribution of 0.3 to 3.0 μm, and an aspect ratio of 1.0 to 3.0 amorphous inorganic compound particles. Proposed sheet. (See Patent Document 1) This amorphous inorganic compound particle selectively scatters near-infrared rays and transmits visible light, thereby making it possible to obtain heat shielding properties and daylighting properties at the same time, and to lose much of the heat shielding properties. It can also be used without coloring. However, even in the heat shield sheet obtained by this technology, the temperature of the sheet itself may rise to close to 60 ° C. under strong summer sunshine, so this heat shield sheet can be used as a support for thin solar cells. The required performance is still unsatisfactory for use, and the internal temperature environment has not been improved significantly even in the tent structure of this sheet. This heat shield sheet expresses a higher heat control function at a level of 10 to 15 ° C. than a conventional sheet, but further improvement of the heat control effect is desired from the viewpoint of energy saving without using an air conditioner. On the other hand, since this thermal insulation sheet scatters near-infrared rays and does not transmit it, it is not suitable for the function of taking solar heat into the tent structure and storing the inside of the structure in winter.

  By containing tungsten oxide, an attempt has been made to obtain a sheet that transmits visible light and has translucency and absorbs near-infrared rays and has heat shielding properties. However, since tungsten oxide absorbs not only near infrared rays but also part of visible light (red to yellow), the sheet containing this is colored (blue or green) and colored. There is no degree of freedom. Moreover, since it is near-infrared shielding by absorption, the temperature rise of a sheet | seat itself cannot be suppressed in the summer and is a sheet | seat unsuitable for using for a thin-film solar cell.

A hexaboride such as LaB ₆ and CeB _6, in combination with inorganic white pigments such as titanium oxide, laminate film comprising a film and an inorganic white pigment containing hexaboride, or the hexaboride and an inorganic white pigment The technique regarding the film containing this together is also disclosed. (For example, see Patent Document 3) According to this method, excellent near-infrared shielding properties can be obtained, but no visible light can be obtained because visible light is also shielded at the same time. In addition, the temperature rise of the sheet itself cannot be suppressed in summer, and the sheet is not suitable for use in a thin solar cell.

In order to adjust the temperature, a method has been disclosed in which a material having a high thermal emissivity at a high temperature and a low thermal emissivity at a low temperature is contained in a fiber or a coating composition (see, for example, Patent Documents 4 and 5). As a substance having such a property, a perovskite oxide containing Mn represented by A _{1 -X} B _X MnO ₃ (A is at least one of rare earth ions of La, Pr, Nd, and Sm, B is Corundum vanadium oxides containing at least one of alkaline earth metal ions of Ca, Sr, and Ba) and Cr are disclosed. These materials undergo a metal-insulator transition at 280 K to 300 K (about 7 ° C. to about 27 ° C.), and have a high thermal emissivity due to the insulating properties above the transition temperature, and heat due to the metallic properties below the transition temperature. It has the property of low emissivity. If these composite oxides are applied to a sheet for a tent structure, when the temperature of the sheet rises above the transition temperature in summer, an effect of lowering the sheet temperature by radiating thermal energy as far infrared rays is expected. In winter, if the weather is fine, the seat temperature rises due to solar radiation, and the effect of keeping it near the transition temperature is expected. However, simply mixing these composite oxide particles into a flexible resin does not sufficiently prevent the transmission of near-infrared rays, and the temperature of the sheet itself can be kept somewhat low in summer. However, the effect of preventing the temperature inside the tent structure from being increased by partially transmitting near infrared rays was not sufficient.

  As described above, so far it has heat insulation in the summer, prevents excessive temperature rise of the seat, can take in a certain amount of heat in clear weather in winter, and also has the freedom of lighting and coloring No heat controllable sheet having

JP 2007-055177 A JP 2009-144037 A JP 2006-340675 A JP 2006-342450 A Japanese Patent No. 3221412

  The present invention prevents excessive heating of the sheet by radiating thermal energy as far-infrared rays in the hot weather in summer and shields near infrared rays to show high heat shielding properties. It is intended to provide a heat-controllable sheet that has little heat radiation by heating or heating, has a heat storage property, and further has daylighting and coloring freedom.

  In order to solve the above problems, the present inventors have intensively studied, as a result, a synthetic resin containing metal-insulator transition material particles having a transition temperature in the range of 10 to 60 ° C., and a near-infrared scattering colorant. By including an incompatible resin layer formed by a sea-island dispersion structure made of a mixture with a synthetic resin as a near-infrared shielding layer, it has summer heat shielding properties, prevents excessive temperature rise of the sheet itself, and The present inventors have found that a sheet having a thermal storage property in winter can be obtained and completed the present invention.

  That is, the heat-controllable sheet of the present invention is a flexible sheet containing a near-infrared shielding layer, and the near-infrared shielding layer comprises a synthetic resin containing metal-insulator transition material particles and a near-infrared scattering colorant. It consists of an incompatible resin layer formed by a sea-island dispersion structure made of a mixture with a synthetic resin. In the heat-controllable sheet of the present invention, the sea component may include the metal-insulator transition material particles and the island component may include the near-infrared scattering colorant in the sea-island dispersion structure. In the heat-controllable sheet of the present invention, in the sea-island dispersion structure, the sea component may include the near-infrared scattering colorant, and the island component may include the metal-insulator transition material particles. In the thermally controllable sheet of the present invention, the metal-insulator transition material particles include a metal composite oxide particle having a perovskite structure and containing manganese, and a metal composite oxide particle having a corundum structure and containing chromium and vanadium, It is preferable that it has a transition temperature in the range of 10-60 degreeC including 1 or more types chosen from these. In the heat-controllable sheet of the present invention, the near-infrared scattering colorant comprises titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, chromium oxide, iron oxide, tin-doped. Metal oxide selected from indium oxide, indium-doped tin oxide, antimony-doped tin oxide, and a rutile, hematite, or spinel structure, titanium, zinc, antimony, iron, nickel, cobalt, chromium, It is preferable to include one or more selected from metal composite oxides containing two or more components of magnesium, copper, manganese, aluminum, niobium, and silicon. In the heat-controllable sheet of the present invention, it is preferable that the flexible sheet is a laminate including a fiber base fabric. In the heat-controllable sheet of the present invention, a flexible solar cell module may be laminated on the outermost surface of the flexible sheet.

  The heat-controllable sheet of the present invention shields near infrared rays and has a high thermal emissivity at high temperatures, thereby quickly radiating heat received from sunlight under the hot summer sun to prevent the temperature of the sheet from increasing. Since the thermal emissivity is low at low temperatures in winter, there is little radiation of heat warmed by sunlight or heating, etc., and it has a heat storage property, and it has daylighting and coloring freedom. The heat controllable sheet with the flexible solar cell module laminated on the outermost layer suppresses the decrease in power generation efficiency due to the temperature rise of the solar cell element in summer, or the expansion and contraction of the solar cell It is possible to prevent the life from being shortened. In addition, this heat-controllable sheet is used in tent warehouses, large tents for events, agricultural and horticultural houses, awning tents, awning monuments, decorative tents, blinds, seat shutters, partitions, truck hoods, etc. It is possible to provide a film structure having a daylighting property that is warm and does not require lighting during the day.

The figure which shows an example of the heat-controllable sheet | seat of this invention The figure which shows an example of the heat-controllable sheet | seat of this invention, and shows the state which a sea component contains a metal-insulator transition material particle and an island component contains a near-infrared-scattering colorant. The figure which shows an example of the heat-controllable sheet of this invention, and shows the state which a sea component contains a near-infrared scattering colorant and an island component contains metal-insulator transition material particles. The figure which shows an example of the heat-controllable sheet | seat of this invention containing the flexible solar cell module laminated | stacked on the outermost surface. The figure which shows the structure which evaluated the temperature rise and temperature fall of the low temperature environment in an Example and a comparative example

  The heat-controllable sheet of the present invention is a flexible sheet including a near-infrared shielding layer, and the form thereof is a resin sheet (resin film), a tarpaulin, a waterproof sheet such as canvas, or a mesh sheet. Among these, the resin sheet can be produced by a calendar molding method, a T-die extrusion method, or a casting method, and may be a single near-infrared shielding layer, or a plurality of resin sheets including a near-infrared shielding layer are laminated. A laminated body may be sufficient. Tarpaulins, waterproof sheets such as canvas, and mesh sheets are laminates including a near-infrared shielding layer and a fiber base fabric, and the near-infrared shielding layer may be formed only on one surface of the fiber base fabric, It may be formed on both sides. Canvas and mesh sheets include flexible resins solubilized in organic solvents, flexible resin emulsions (latex) emulsion-polymerized in water, or dispersion resins stabilized by forcibly dispersing flexible resins in water Can be produced by dipping using a water-dispersed resin, soft polyvinyl chloride resin paste sol, etc. (double-sided processing on a fiber fabric), coating processing (single-sided processing or double-sided processing on a fiber fabric), and the like. Tarpaulin is a method of laminating a resin film or resin sheet molded by a calendar molding method, a T-die extrusion method or a casting method with an adhesive layer on one or both sides of a fiber base fabric, or a coarse fiber base fabric. It is preferable to manufacture by the method of carrying out heat lamination lamination | stacking through a void | interval void | hole part on both surfaces, and also it can implement by the combination of dipping processing or coating processing, and resin film lamination. In the case of the resin sheet, tarpaulin, and canvas, the heat-controllable sheet of the present invention has a visible light transmittance (JISZ8722.5.4 (condition g)) of 3 to 35%, and is a transparent resin sheet, a transparent tarpaulin, and a mesh sheet. In some cases, 10 to 80% is preferable.

  In order to impart strength, durability, dimensional stability, etc., the heat-controllable sheet of the present invention is preferably a laminate containing a fiber base fabric, specifically, the above-mentioned tarpaulin, canvas, and mesh sheet. . As fibers used for the fiber base fabric, polypropylene fibers, polyethylene fibers, polyester fibers, nylon fibers, vinylon fibers and other synthetic fibers, cotton, hemp and other natural fibers, acetate and other semi-synthetic fibers, glass fibers, silica fibers, Examples thereof include inorganic fibers such as alumina fibers and carbon fibers, and these may be composed of single or a mixture of two or more kinds. The shape may be any of multifilament yarn, short fiber spun yarn, monofilament yarn, split yarn yarn, tape yarn yarn and the like. The fiber base fabric used in the present invention may be any of woven fabric, knitted fabric and non-woven fabric. When a woven fabric is used, it may have any structure such as a plain weave, twill weave, satin weave, or patterned weave, but a plain weave fabric is preferably used because it has an excellent balance of physical properties of the resulting heat-controllable sheet. When using a knitted fabric, a weft insertion tricot of Russell knitting is preferably used. These knitted fabrics are each a coarse knitted fabric composed of yarns including warps and wefts arranged in parallel with a gap between yarns (the porosity is 90% at maximum, preferably 5 to 50%) And non-coarse knitted fabric (knitted fabric with substantially no gap formed between yarns). As the nonwoven fabric, a spunbond nonwoven fabric can be used. The fiber base fabric may be subjected to water repellent treatment, water absorption prevention treatment, adhesion treatment, flame retardant treatment, and the like as necessary.

Of these, a non-coarse knitted fabric made of inorganic fibers such as glass fiber, silica fiber, and alumina fiber is used as a fiber base fabric, thereby obtaining a heat-controllable sheet having incombustibility as defined in the Building Standards Act. It becomes possible. Specifically, in an exothermic test (ASTM-E1354: corn calorimeter test method) in which radiant heat of 50 kW / m ² is irradiated using a radiant electric heater, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ^2. And a non-flammable heat controllable sheet satisfying that the maximum heat generation rate continues for 10 seconds or more and does not exceed 200 kW / m ² for 20 minutes after the start of heating. It can be obtained by providing a near-infrared shielding layer on one or more sides of a fiber base fabric having a mass of 200 to 300 g / m ² and a porosity of 1% or less. In addition, the use of a fiber base made of inorganic fibers improves dimensional stability, and when the heat-controllable sheet contains a flexible solar cell module, the module may be damaged by expansion and contraction due to temperature changes. Can be suppressed.

  In the present invention, the near-infrared shielding layer is molded by a known processing method by melting a synthetic resin blend or by stirring a liquid synthetic resin in a synthetic resin blend. Synthetic resins preferably used in the present invention include, for example, vinyl chloride resins, vinyl chloride copolymer resins, olefin resins (polyethylene, polypropylene, etc.), olefin copolymer resins, urethane resins, and urethane copolymer resins. , Acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, styrene resin, styrene copolymer resin, polyester resin (PET, PEN, PBT, etc.), polyester copolymer resin Fluorine-containing copolymer resin, silicone resin, silicone rubber, polycarbonate, polyamide, polyether, polyesteramide, polyphenylene sulfide, polyetherester, vinylester resin, unsaturated polyester resin, etc. Thermoplastic resin with Curable resin is preferably used.

  The near-infrared shielding layer of the present invention is an incompatible resin layer formed by a sea-island dispersion structure made of a synthetic resin mixture, and the combination of synthetic resins to be mixed is not particularly limited as long as it is incompatible. Incompatible combinations include vinyl chloride resin and polyethylene, vinyl chloride resin and polypropylene, vinyl chloride resin and styrene resin, vinyl chloride resin and styrene copolymer resin, vinyl chloride resin and silicone resin, vinyl chloride resin and fluorine. Containing copolymer resin, vinyl chloride resin and vinyl ester resin, styrene resin and polyethylene, styrene resin and polypropylene, urethane resin and polyethylene, urethane resin and polypropylene, polyester resin and polyethylene, polyester resin and polypropylene, polyamide and polycarbonate, acrylic resin And incompatible flexible resin pairs such as styrene resin, acrylic resin and polycarbonate, polyamide and styrene resin, and polyamide and polypropylene. Moreover, another kind of flexible resin can also be contained with respect to these incompatible flexible resin pairs.

  These incompatible resin layers preferably have a sea-island dispersion structure with a cloudy appearance showing a phase separation structure. In this sea-island dispersion structure, the sea component and the island component are composed of different types of resins. For example, in an incompatible mixture composed of synthetic resin A and synthetic resin B, the sea component is set by setting the ratio of synthetic resin A and synthetic resin B. Can be composed of the synthetic resin A, the island component can be composed of the synthetic resin B, the sea component can be composed of the synthetic resin B, and the island component can be composed of the synthetic resin A. Here, the near-infrared shielding layer has a sea-island dispersion structure, and either the sea component or the island component contains metal-insulator transition material particles, and the other contains a near-infrared scattering colorant, In summer, heat received from sunlight is radiated to prevent excessive temperature rise of the sheet, and near-infrared rays are shielded to show heat insulation. In winter, the sheet is heated by sunlight or heating. Therefore, a heat controllable sheet having a low heat radiation property, a heat storage property, a daylighting property, and a coloring degree of freedom can be obtained. The ratio of the synthetic resin constituting the island component is preferably 3 to 50% by volume, more preferably 5 to 40% by volume with respect to the volume of the synthetic resin constituting the sea component. 2.9-33.3 volume% is preferable and, as for the island component content rate with respect to the whole near-infrared shielding layer which has a sea-island dispersion | distribution structure, 4.7-28.6 volume% is more preferable. If the island component content relative to the entire near-infrared shielding layer having a sea-island dispersion structure is less than 2.9% by volume, there is no difference from the case without the sea-island dispersion structure, and the effects of the present invention cannot be sufficiently obtained. . That is, when the sea component contains metal-insulator transition material particles, the near-infrared shielding property may be insufficient, and when the sea component contains a near-infrared scattering colorant, the effect of radiating thermal energy as far-infrared rays is effective. There may be a shortage. On the other hand, if the island component content with respect to the entire near-infrared shielding layer exceeds 33.3% by volume, the resin strength of the near-infrared shielding layer is lowered, and the strength and durability of the resulting sheet are lowered. Moreover, in this invention, it is preferable that the average particle diameter of the island component in a sea-island dispersion structure is 0.4-20 micrometers. When the average particle diameter of the island component is within this range, a near-infrared refractive scattering phenomenon occurs at the interface between the sea component and the island component, and the near-infrared scattering in the near-infrared shielding layer increases. When the average particle size of the island component is less than 0.4 μm, the light scattering increases in part of the visible light due to the refraction and scattering phenomenon at the interface, and the visible light transmittance decreases, or a specific wavelength within the visible light region. The near-infrared shielding layer may appear to be colored by scattering the light. When the average particle diameter of the island component exceeds 20 μm, the visible light transmittance may be lowered due to scattering over the entire visible light region. In addition, when another type of flexible resin C is contained in the incompatible flexible resin pair AB, the island component is composed of the flexible resin B and the flexible resin in the sea-island dispersion structure. The island component by C may be comprised, and the island component by the flexible resin A and the island component by the flexible resin C may be comprised similarly. In the present invention, the thickness of the near-infrared shielding layer having a sea-island dispersion structure is preferably 0.03 to 1.0 mm, and more preferably 0.05 to 0.5 mm. If the thickness of the near-infrared shielding layer is less than 0.03 mm, sufficient thermal controllability may not be obtained, and if it exceeds 1.0 mm, the visible light transmittance is reduced or a flexible sheet cannot be obtained. Sometimes.

As the metal-insulator transition material particles used in the present invention, one or more of the following (A) and (B) can be selected and used.
(A) has a perovskite structure and contains manganese (Mn);
(A _1-x B _x ) Mn _{1 + y} O ₃ (where A is one or more selected from the group consisting of La, Pr, Nd and Sm rare earth elements, and B is an alkaline earth of Ca, Sr and Ba) 1 or 2 or more selected from the group of metals).
(B) has a corundum structure and contains chromium (Cr) and vanadium (V);
Metal composite oxide particles represented by (V _1-X Cr _X ) ₂ O ₃ and 0 ≦ x <1.
The metal-insulator transition material particles used in the present invention express an insulating property at a temperature higher than that temperature at a specific temperature, and increase the amount of heat radiation. This is a metal composite oxide particle that exhibits properties and reduces the amount of heat radiation. In the present invention, the resin layer containing these metal-insulator transition material particles in the sea component or island component in the sea-island dispersion structure is exposed to solar radiation in summer, and the temperature of the resin containing these particles is higher than the transition temperature. When the temperature rises, the heat is emitted as far-infrared rays to lower the resin temperature. In winter, the amount of radiation is small in the range where the resin temperature does not reach the transition temperature, making it difficult to release the heat received from solar radiation. Can show gender. In the present invention, the transition temperature of the metal-insulator transition material particles is preferably in the range of 10 to 60 ° C. The transition temperature can be changed according to the type of element to be selected and the values of x and y in the above formula. In order to have the transition temperature within this range, x and y are respectively 0 ≦ x <1, 0 ≦ y. It is preferable that ≦ 0.1. In the present invention, the metal-insulator transition material particles are preferably contained in an amount of 0.01 to 30% by mass and preferably 0.1 to 15% by mass with respect to the synthetic resin constituting the sea component or island component. More preferred. If it is less than 0.01% by mass, the effect of addition is insufficient, and sufficient thermal controllability may not be obtained. When it exceeds 30 mass%, workability and resin strength may decrease, or the visible light transmittance of the resulting heat-controllable sheet may decrease. In the present invention, the particle size of the metal-insulator transition material particles to be used is not particularly limited, but is appropriately selected from particles having an average particle size of 1 to 1000 nm in consideration of dispersibility in a resin, processability of a sheet, and the like. Can be used. In particular, in order to increase the transmittance of visible light, particles having an average particle diameter of 2 to 400 nm are preferable, and 2 to 200 nm is more preferable. These metal-insulator transition material particles have an azo, anthraquinone, phthalocyanine, perinone / perylene, indigo / thioindigo, dioxazine that has little absorption in the near infrared region on its surface and absorption in the visible light region. It may be coated with at least one selected from the group consisting of organic, quinacridone, isoindolinone, isoindoline, diketopyrrolopyrrole, azomethine and azomethine azo organic dyes. In order to improve the dispersibility in the resin, the surface may be coated with an oxide containing one or more metals selected from Si, Zr, and Al, or a higher fatty acid. .

  The near-infrared scattering colorant used in the present invention can be appropriately selected from inorganic colorants having the property of scattering near-infrared rays, such as metal particles, metal oxide particles, and metal composite oxide particles. Can be illustrated. By including these particles in the sea component or island component in the sea-island dispersion structure, near-infrared rays are scattered inside the near-infrared shielding layer, reducing the near-infrared transmittance of the sheet, and the other side of the sea-island dispersion structure. This makes it easy to incorporate heat from solar radiation into the resin and improves the heat controllability. Metal particles and metal oxide particles include aluminum, stainless steel, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, manganese oxide, barium oxide, tin oxide, zirconium oxide, indium oxide, Antimony trioxide, chromium oxide, iron oxide, copper oxide, molybdenum oxide, cobalt oxide, yttrium oxide, cerium oxide, bismuth oxide, silicon oxide, tin-doped indium oxide, indium-doped tin oxide, and Examples include particles made of antimony-doped tin oxide, among which titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, chromium oxide, iron oxide, tin-doped oxide Indium, indium doped tin oxide and antimony Infrared scattering effect of doped tin oxide is high, is preferably used. These metal particles and metal oxide particles are azo, anthraquinone, phthalocyanine, perinone / perylene, indigo / thioindigo, dioxazine that has little absorption in the near infrared region on the surface and absorption in the visible light region. It may be coated with at least one selected from the group consisting of organic, quinacridone, isoindolinone, isoindoline, diketopyrrolopyrrole, azomethine and azomethine azo organic dyes. In addition, in order to suppress the photocatalytic activity of particles having photocatalytic activity or to improve the dispersibility in the resin, the surface of the oxide contains one or more metals selected from Si, Zr, and Al. Or what was coat | covered with the higher fatty acid etc. may be used. Examples of the metal composite oxide particles include titanium (Ti), zinc (Zn), antimony (Sb), iron (Fe), nickel (Ni), cobalt (Co), chromium (Cr), magnesium (Mg), copper ( Cu), manganese (Mn), aluminum (Al), niobium (Nb), and metal composite oxide particles containing two or more components of silicon (Si) can be used. As long as it contains more than one species, metal composite oxide particles further containing components other than those described above can also be used. Specifically, for example, Co-Al, Co-Al-Cr, Co-Al-Cr-Ti, Co-Mg-Sn, Co-Ni-Ti, Co-Zn-Ni-Ti, Co-Zn-Cr- Ti, Co-Sb-Ni-Ti, Co-Nb-Ni-Ti, Nb-Ni-Ti, Co-Si, Sn-Cr-Ti, Zn-Cr-Ti, Zn-Cr-Fe, Co-Zn- Cr-Fe, Co-Ni-Cr-Fe-Si, Co-Cr-Mg-Zn-Al, Co-Mn-Cr-Fe, Co-Fe-Cr, Co-Cr-Ni, Co-Cr, Cu- Mn—Cr, Cu—Mn—Fe, Cu—Cr, Mn—Fe, Zn—Fe, Cr—Fe, Cr—Fe—Zn—Ti, Pb—Sb—Fe, Pb—Sb—Al, Ni—Sb, Fe-Zn-Ti, Fe-Al-Ti, Fe-Ti, Fe-Mo, Cr- b, composite oxide particles comprising components such as Cr—Sb—Ti, Mn—Sb—Ti, Ti—Sb—Ni, Cr—Sn, Fe—Co—Mn—Ni, Ti—Sb—Cr and Zr—Fe Can be illustrated. These metal composite oxide particles have a rutile type, hematite type, or spinel type structure and are commercially available as infrared reflective pigments, and particles having a desired hue are used alone or in combination of two or more. In order to suppress the photocatalytic property and improve the dispersibility in the resin, the surface of the oxide contains one or more metals selected from Si, Zr and Al, or higher fatty acids. You may use what was coat | covered with etc.

  In the present invention, the near-infrared scattering colorant is preferably contained in an amount of 0.05 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the synthetic resin constituting the sea component or the island component. . If it is less than 0.05% by mass, the effect of addition is insufficient and sufficient thermal controllability may not be obtained. When it exceeds 20 mass%, workability and resin strength are reduced, and the visible light transmittance of the resulting heat-controllable sheet may be reduced. In the present invention, the particle diameter of the near-infrared scattering colorant to be used is not particularly limited, but is appropriately selected from particles having an average particle diameter of 1 to 3000 nm in consideration of dispersibility in a resin, processability of a sheet, and the like. Can be used. In particular, in order to further increase near-infrared scattering, particles having an average particle diameter of 350 to 2000 nm are preferable, and 400 to 1600 nm is more preferable. Moreover, particles having an average particle diameter of 20 to 100 nm are preferably used in order to increase the visible light transmittance and obtain a transparent near-infrared shielding layer.

In the sea-island dispersion structure of the near-infrared shielding layer of the present invention, (i) the sea component contains metal-insulator transition material particles, the island component contains a near-infrared scattering colorant, and (ii) the sea component scatters near-infrared. Any of the constitutions including a colorant and the island component including metal-insulator transition material particles may be employed. Although it is not certain about the factor which can obtain thermal controllability by these structures, in the case of the structure of (i), for example, it is guessed as follows.
(A) When the near-infrared shielding layer receives sunlight, the near-infrared light contained in the sunlight is partially absorbed by the metal-insulator transition material particles contained in the sea component, partially scattered, and the rest is the sea Permeates the component.
(B) Most of the near infrared light scattered by the sea component and the near infrared light transmitted through the sea component are scattered by the island component containing the near infrared scattering colorant and returned to the sea component. Near-infrared rays returned to the sea component are partly absorbed again, partly scattered, and the rest penetrating the sea component. By repeating this, a lot of near infrared rays are absorbed by the sea component, and only a small amount of near infrared rays are transmitted through the near infrared shielding layer, so that a heat shielding property is obtained.
(C) The near-infrared shielding layer gradually increases in temperature as the sea component absorbs near-infrared rays,
Until it reaches the transition temperature of the metal-insulator transition material, there is little heat radiation and it has thermal storage properties.
(D) When the temperature of the near-infrared shielding layer exceeds the transition temperature, the amount of heat energy radiated as far-infrared rays increases, reaches an equilibrium with the amount of heat absorbed from sunlight at a certain temperature, and the temperature of the heat-controllable sheet Prevent further rise.
The configurations (i) and (ii) described above prevent excessive temperature rise of the sheet under the hot weather in summer, shield near-infrared rays, have excellent heat shielding properties, and the temperature of the heat-controllable sheet in winter When the temperature is low, there is little heat radiation from the sheet and it has a heat storage property. However, in the comparison between the two, (i) has better winter heat storage property than (ii), and (ii) has a better summer barrier than (i). It has excellent thermal properties. Therefore, it is only necessary to appropriately select and employ the configurations (i) and (ii) according to the region and application in which the heat-controllable sheet of the present invention is used.

  The heat-controllable sheet of the present invention preferably has an antifouling layer on the outermost surface of the flexible sheet in order to maintain heat-controllability, prevent deterioration of daylighting, and maintain aesthetics. The antifouling layer is not particularly limited in its formation method and material as long as it does not impair thermal controllability and daylighting property and does not have extreme concealing properties. Such an antifouling layer is, for example, a coating film formed by applying a resin solution or a resin dispersion composed of at least one of an acrylic resin or a fluorine resin solubilized in a solvent, silica fine particles, or A coating containing colloidal silica, a coating containing an organosilicate and / or its condensate to form a hydrophilic coating layer, a coating containing a photocatalytic inorganic material (eg photocatalytic titanium oxide) and a binder It can be appropriately selected from those in which a photocatalyst layer is formed by applying an agent, and those obtained by laminating a film having at least the outermost surface formed of a fluororesin by an adhesive or hot melt processing.

  In the heat-controllable sheet of the present invention, if necessary, in addition to the antifouling layer, an adhesive layer for improving the adhesion of the antifouling layer, and when the antifouling layer is a photocatalytic layer, the resin is decomposed by the photocatalyst. A protective layer for preventing the additive, an additive transfer preventing layer for preventing the additive contained in the near-infrared shielding layer and / or other resin layer from transferring to the antifouling layer, and the like may be formed. Further, a back surface adhesive layer for imparting high-frequency heat fusion property and hot air fusion property to the antifouling layer on the surface opposite to the surface on which the antifouling layer is formed of the heat controllable sheet of the present invention. It may be formed. Alternatively, in order to prevent the additive contained in the resin layer on the back side from moving on the antifouling layer and reducing the antifouling property while the heat controllable sheet is wound and stored in a roll shape In addition, an additive migration preventing layer may be formed on the back surface side (the surface opposite to the antifouling layer).

  In the heat-controllable sheet of the present invention, the near-infrared shielding layer may additionally contain a known additive as required independently of each of the sea component and the island component. Examples of additives include organic pigments, phosphorescent pigments, fluorescent whitening agents, fluorescent pigments, antistatic agents, flame retardants, plasticizers, flexibility imparting agents, fillers, adhesives, cross-linking agents, UV absorbers, Examples thereof include antioxidants, stabilizers, lubricants, processing aids, leveling agents, antifoaming agents, antibacterial agents, and antifungal agents.

  Next, a configuration example of the heat controllable sheet of the present invention and effects when it is applied to a structure will be described with reference to the drawings.

  When the heat-controllable sheet of the present invention is used for an agricultural or horticultural house, as shown in FIG. 1, only the near-infrared shielding layer (2) is advantageous in increasing the visible light transmittance. In order to give, you may include a base fabric with a large mesh. In the sea-island dispersion structure of the near-infrared shielding layer, the sea component (4-2) contains metal-insulator transition material particles having a transition temperature of 10 to 60 ° C., and the near-infrared scattering colorant is contained in the island component (3-1). Including in summer the temperature inside the house is suppressed to reduce the work of extending the shading sheet, etc., and in the winter the heat inside the house heated by solar energy or heating is heated to the surface of the heat-controllable sheet Suppresses radiation. Furthermore, the plant can be grown throughout the year by transmitting visible light. In addition, in the stage of warming from a low temperature, heat radiation is low below the transition temperature of the metal-insulator transition material, and the heat-controllable sheet heats up quickly in the morning sun, so morning dew condensation can be done in a short time. Eliminate. If a heating device, preferably a heating device that irradiates near infrared rays, is used for the heat-controllable sheet as necessary, the sheet temperature is likely to rise, and condensation at night or in cloudy weather can be prevented. In contrast to FIG. 1, the sea component may include a near-infrared scattering colorant, and the island component may include metal-insulator transition material particles having a transition temperature of 10 to 60 ° C.

  When the heat-controllable sheet of the present invention is used in a tent warehouse, a tent having excellent strength and durability can be obtained by using the heat-controllable sheet (1) including the fiber base fabric (5) as shown in FIGS. A warehouse is obtained. The heat controllable sheet of the present invention, unlike a conventional heat shield sheet that reflects near infrared rays, absorbs near infrared rays and exhibits heat shielding properties, and radiates its thermal energy as far infrared rays to excessively increase the sheet temperature. Therefore, even if dirt is attached to the surface, there is not much influence on the heat insulation in summer. However, when dirt adheres, the effect of suppressing far-infrared radiation at low temperatures may be impaired, and further, the daylighting property is lowered and the aesthetic appearance is also impaired. Therefore, it is preferable to further have an antifouling layer (8) on the outermost surface. In the sea-island dispersion structure of the near-infrared shielding layer, the sea component or island component contains metal-insulator transition material particles having a transition temperature of 10 to 60 ° C., and the other side of the sea component or island component is colored by near-infrared scattering The inclusion of the agent improves the working environment by preventing the temperature inside the tent warehouse from rising during summer sunshine. Further, since the heat-controllable sheet of the present invention has less radiation below the transition temperature of the metal-insulator transition material particles and the decrease in the sheet temperature is gradual, condensation at night hardly occurs. On the other hand, heat energy from sunlight is taken into the tent warehouse during the winter, and a warm environment can be obtained during sunshine. Heating during heating is used from the surface of the heat-controllable sheet when heating is used during cloudy weather or at night. Radiation is suppressed and heating efficiency can be increased.

  FIG. 4 is an example of a thermally controllable sheet (1) in which a flexible solar cell module (7) is laminated on the outermost surface of the flexible sheet of the present invention (details of the flexible solar cell module are omitted). ). The solar cell elements included in the flexible solar cell module are of a crystalline silicon type and an amorphous silicon type and have different characteristics. Therefore, a thermally controllable sheet that matches each characteristic is required. First, since the crystalline silicon type has a problem that the output decreases when the temperature rises, the heat controllable sheet is required to suppress the temperature rise particularly in summer. Therefore, it has a near-infrared shielding layer that contains metal-insulator transition material particles having a relatively low transition temperature in the range of 10 to 60 ° C., for example, 30 ° C. or less as a sea component and a near-infrared scattering colorant as an island component. If it comprises, the amount of thermal energy radiated | emitted as a far infrared ray in the temperature exceeding 30 degreeC will increase, the temperature of a heat-controllable sheet will be kept low (for example, 60 degrees C or less), and the output fall by a temperature rise will be suppressed. I can do things. On the other hand, the amorphous silicon type has a low output at a low temperature, and the output increases as the temperature rises. Therefore, it is required to raise the temperature by being exposed to sunlight in winter. Therefore, the transition temperature is relatively high in the range of 10 to 60 ° C., for example, it has a near-infrared shielding layer containing metal-insulator transition material particles exceeding 30 ° C. as a sea component and an island component containing a near-infrared scattering colorant. If it is set as a structure, near infrared rays contained in solar radiation will be absorbed at a temperature of 30 ° C. or lower, and the temperature will easily rise, and the output can be kept high. In addition, since the heat-controllable sheet including the fiber base fabric (5) is reinforced by the fiber base fabric, the solar cell module can be repeatedly expanded and contracted even if the temperature difference between daytime and nighttime is large. It is possible to prevent damage and prolong the life as a solar cell, and it can be used as a part of a film structure such as a tent warehouse, a large tent for an event, and an awning.

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

With respect to the sheets obtained in the following examples and comparative examples, the heat shielding rate, the surface temperature, the heat storage property, the near-infrared shielding property, and the visible light transmittance were evaluated by the following test methods.
<Heat insulation rate>
Test environment: An incandescent lamp (100V) at the center of the ceiling of a box-type structure that has an inner diameter of 45cm x width 35cm x length 35cm, has an outside temperature blocking property and airtightness, and has a door that can be opened and closed on the side. , 5
Attach a 00W photo reflector lamp (for daylight color: manufactured by Toshiba Corporation)
At the center of the bottom of the box structure, a sensor of a heat flow meter (Shotrm HFM heat flow meter: Showa Denko Co., Ltd.) is attached and fixed, and this box structure is installed in a constant temperature room at 20 ° C. The test environment for thermal insulation evaluation was configured.
Test: The outer diameter of 5cm in height x 10cm in width x 15cm in length by fixing a square rod made of acrylic resin with a square section of 0.5cm as a pillar and beam with instantaneous adhesive. Assemble the box-type frame that has the structure, attach this box-type frame to the center of the bottom part of the box-type structure (on the heat flow meter sensor), close the door of the box-type structure to make it sealed, and heat flow without seat (Kcal / m ² h) was measured every minute, and the heat flow qn (kcal / m ² h) after 30 minutes was measured.
After measuring the heat flow qn, the box-type structure door was opened until the internal temperature was stabilized at 20 ° C., which is the same as the temperature-controlled room. Next, the sheets created in the examples and comparative examples are affixed to the four side surfaces of the box-type frame and the top surface (ceiling) with double-sided tape so that the front surface faces outward. A test box with a bottom surface was prepared. The test box with the sheet attached was attached to the center of the bottom of the box-type structure, and fixed so that the direction of the straight line connecting the center point of the lamp and the center point of the test box overlapped in the vertical direction. The distance from the lamp tip inside the box structure to the ceiling part (sheet front surface) of the test box was 35 cm. Close the door of the box structure and place it in a sealed state, turn on the lamp, measure the heat flow (kcal / m ² h) every minute, heat flow after 30 minutes qc (kcal / m ² h) Was measured, and the heat shielding rate was determined by the following formula. The heat insulation rate was judged to be higher as the value was higher.
Heat shielding rate (%) = [(qn−qc) / qn] × 100
In addition to the initial heat insulation, the sheet containing the fiber base fabric was also measured one year after outdoor exposure.
Outdoor exposure:
On the outdoor exposure table, a one-year outdoor exposure test was conducted with the sheet prepared in the example and the comparative example facing upward with an inclination angle of 30 degrees facing south.
Location: Soka, Saitama Period: June 1, 2009 to May 31, 2010 <Surface temperature>
Test: After measuring the heat flow rate qc of the above heat insulation rate, the surface temperature of the center part of the front side of the ceiling is promptly measured using a contact type surface thermometer using a thermocouple sensor (manufactured by Testo Co., Ltd.). TT-905-T
It was measured by 2).
<Temperature rise and fall in low-temperature environments (thermal storage)>
Test environment (see FIG. 5): Sheet (1) prepared in Examples and Comparative Examples was cut into a 20 cm square, and a surface temperature sensor (9: Mitsubishi Materials Corp. STS-60) was attached to the center of the back side. (Not shown). Next, prepare a 20 cm wide, 20 cm wide, 5 cm thick foamed polystyrene board (10), with the front side of the sheet (1) facing up, and stick it to the foamed polystyrene board so that the four sides do not float. The sample for measurement (11) was left standing in a cold storage warehouse at 5 ° C. for 24 hours or longer. Sample for measurement (11)
Place the sheet (1) on the floor and place it horizontally on the floor of the cold storage warehouse. The distance between the sheet front surface and the lamp tip is 30 cm, and the lamp center point and the sheet center point are connected. A halogen lamp (12: 100 V, 85 W relamp type, manufactured by Ushio Lighting Co., Ltd.) was fixed so that the direction of the straight line overlapped with the vertical direction.
Test: Turn on the halogen lamp, observe the temperature with the surface temperature sensor attached to the back of the sheet, measure the temperature rise time until it reaches 30 ° C, and then quickly turn on the halogen lamp when it reaches 30 ° C. The temperature was lowered until the temperature decreased to 15 ° C. (minutes).
It was judged that a sheet having a high temperature storage time and a long temperature decrease time was a sheet having a high temperature storage property.
In addition to the initial heat storage, the sheet containing fiber base fabric was also measured one year after outdoor exposure. (Exposure was performed under the same conditions as the above <heat shielding rate>)
<Near-infrared shielding>
Using Shimadzu UV-3600, with the sheet front facing the light source, the wavelength 1000n
The near infrared transmittance of m was measured.
It was judged that the near-infrared shielding property was higher as the transmittance was lower.
<Visible light transmittance (lighting property)>
According to JIS Z8722.5.4 (condition g), using a Minolta spectrocolorimeter CM-3600d,
Visible light transmittance was measured.
A material having a high visible light transmittance was judged to be excellent in daylighting.

[Example 1]
A hot-melt kneaded product of a styrene butadiene block copolymer (SBS) containing a near-infrared scattering colorant of the following formulation 2 was added to a soft-melt kneaded product of the following compound 1 containing metal-insulator transition material particles-containing soft vinyl chloride resin. An incompatible resin mixture 1 was obtained in which 20% by mass relative to the mass of the single substance was added and heat-melted and kneaded with a Banbury mixer to uniformly disperse the styrene-butadiene block copolymer in the soft vinyl chloride resin. _{Formula 1 uses} perovskite oxide (La _0.825 Sr _0.175 MnO ₃ : transition temperature 17 ° C.) particles having an average particle size of 200 nm as metal-insulator transition material particles, and _Formula 2 uses near-infrared scattering colorants. The titanium oxide particles having an average particle diameter of 1000 nm were used. This incompatible resin mixture 1 was passed through four calendar rolls set at 180 ° C. to mold a white heat-controllable sheet comprising a near-infrared shielding layer having a thickness of 0.3 mm. When this near-infrared shielding layer was observed with a microscope, the near-infrared scattering colorant-containing styrene butadiene block copolymer constituted an island component, and the metal-insulator transition material particle-containing soft vinyl chloride resin constituted a sea component. The average particle size of the island components in the sea-island dispersion structure was 7.2 μm. Since this heat-controllable sheet has no difference between the front and back, various evaluations were performed with a mark on one surface and the surface as the front surface. The results are shown in Table 1.
<Formulation 1>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 60 parts by mass Tricresyl phosphate (plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate ( Stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Ultraviolet absorber: Benzotriazole series 0.5 part by mass La _0.825 Sr _0.175 MnO _3: Average particle diameter 200 nm 5 parts by mass

<Formulation 2>
100 parts by mass of styrene / butadiene block copolymer (product name: Asaflex 830, manufactured by Asahi Kasei Chemicals Corporation)
Titanium oxide: average particle size 1000 nm 5 parts by mass

[Example 2]
The heat-melt kneaded product of the soft vinyl chloride resin containing the near-infrared scattering colorant containing the following formulation 3 and the styrene-butadiene block copolymer containing the metal-insulator transition material particles shown in the following formulation 4 are added to the mass of the vinyl chloride resin alone. 20 mass% was added, and it was heat-melt-kneaded with the Banbury mixer, and the incompatible resin mixture 2 in which the styrene butadiene block copolymer was uniformly dispersed was obtained. Formulation 3 uses titanium oxide with an average particle size of 1000 nm as a near-infrared scattering colorant, and Formulation 4 uses a perovskite oxide (La _0.825 Sr _0.175 MnO with an average particle size of 200 nm as metal-insulator transition material particles). ₃ : transition temperature 17 ° C.) particles were used. This incompatible resin mixture 2 was passed through four calender rolls set at 180 ° C. to mold a white heat-controllable sheet comprising a near-infrared shielding layer having a thickness of 0.3 mm. When the near-infrared shielding layer was observed with a microscope, the styrene-butadiene block copolymer containing metal-insulator transition material particles constituted an island component, and the near-infrared scattering colorant-containing soft vinyl chloride resin constituted a sea component. The average particle size of the island components in the sea-island dispersion structure was 7.2 μm. Since this heat-controllable sheet has no difference between the front and back, various evaluations were performed with a mark on one surface and the surface as the front surface. The results are shown in Table 1.
<Formulation 3>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 60 parts by mass Tricresyl phosphate (plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate ( Stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight UV absorber: benzotriazole series 0.5 parts by weight Titanium oxide: average particle size 1000 nm 3 parts by weight

<Formulation 4>
100 parts by mass of styrene / butadiene block copolymer (product name: Asaflex 830, manufactured by Asahi Kasei Chemicals Corporation)
La _0.825 Sr _0.175 MnO _3: average particle diameter 200 nm 10 parts by mass

[Example 3]
Implementation was performed except that the metal-insulator transition material particles in Formula ₁ were replaced with perovskite oxide ((La _0.78 Sr _0.12 Ca _0.1 ) MnO ₃ ) particles having a transition temperature of 47 ° C. and an average particle size of 200 nm. A thermally controllable sheet was obtained in the same manner as in Example 1. Since this heat-controllable sheet has no difference between the front and back, various evaluations were performed with a mark on one surface and the surface as the front surface. The results are shown in Table 1.

  The heat-controllable sheets of Examples 1 to 3 are incompatible with each other formed by a sea-island dispersion structure composed of a mixture of a synthetic resin containing metal-insulator transition material particles and a synthetic resin containing a near-infrared scattering colorant. By having a resin layer, all were sheets excellent in heat controllability and daylighting. Comparing Example 1 in which the metal-insulator transition material particles are included in the sea component and Example 2 in which the island component is included in the island component, Example 1 has a lower surface temperature after the measurement of the heat shielding rate than Example 2, and the low temperature. The temperature rise at the time was excellent, and Example 2 was a result of higher heat shielding properties than Example 1. In addition, Example 3 using a metal-insulator transition material having a high transition temperature is superior in temperature rising / falling at a low temperature as compared to Example 1, while Example 1 is shielded compared to Example 3. The results were excellent in thermal properties, and the surface temperature after the measurement of the heat shielding rate was low.

[Comparative Example 1]
A hot melt kneaded product of the soft vinyl chloride resin containing metal-insulator transition material particles of Formulation 1 was passed through four calender rolls set at 180 ° C. to form a milky white sheet having a thickness of 0.3 mm. Since this sheet does not have a difference between the front and back sides, a mark was provided on one surface, and various evaluations were performed using that surface as a front surface. The results are shown in Table 1.

  The sheet of Comparative Example 1 does not have a sea-island structure, and is a sheet containing metal-insulator transition material particles as a whole. Although the daylighting property is higher than those of Examples 1 to 3, the near-infrared shielding property is low. Thermal properties were inferior.

[Comparative Example 2]
A hot melt kneaded product of the near-infrared scattering colorant-containing soft vinyl chloride resin of Formulation 3 was passed through four calendar rolls set at 180 ° C. to form a white sheet having a thickness of 0.3 mm. Since this sheet does not have a difference between the front and back sides, a mark was provided on one surface, and various evaluations were performed using that surface as a front surface. The results are shown in Table 1.

  The sheet of Comparative Example 2 does not have a sea-island structure and is a sheet containing a near-infrared scattering colorant as a whole and has a high near-infrared shielding property and a thermal insulation property equivalent to that of Example 1, but scatters near-infrared rays. Therefore, the sheet did not absorb near infrared rays so much, and it took time to raise the temperature at a low temperature.

[Comparative Example 3]
Heat-kneaded kneaded product of metal-insulator transition material particles / near-infrared scattering colorant-containing soft vinyl chloride resin of the following formulation 5 was passed through four calendar rolls set at 180 ° C. A sheet was molded. In _{Formula 5} , perovskite oxide (La _0.825 Sr _0.175 MnO ₃ : transition temperature 17 ° C.) particles having an average particle size of 200 nm as metal-insulator transition material particles, and an average particle size of 1000 nm as a near-infrared scattering colorant. Titanium oxide was used. Since this sheet does not have a difference between the front and back sides, a mark was provided on one surface, and various evaluations were performed using that surface as a front surface. The results are shown in Table 1.
<Formulation 5>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 60 parts by mass Tricresyl phosphate (plasticizer) 10 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Zinc stearate ( Stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass UV absorber: benzotriazole 0.5 part by mass La _0.825 Sr _0.175 MnO ₃ : average particle size 200 nm 4.3 parts by mass Titanium oxide : Average particle size 1000 nm 0.9 parts by mass

  The sheet of Comparative Example 3 does not have a sea-island structure, and is a sheet containing metal-insulator transition material particles and a near-infrared scattering colorant as a whole, and the content per unit area of the sheet is as in Example 1. Although it was equivalent, both the heat shielding properties and the temperature rise at low temperatures were inferior to those of Example 1. This is because, in Comparative Example 3, near-infrared scattering in the sheet is only due to the near-infrared scattering colorant, whereas in Example 1, near-infrared light is scattered also at the sea-island interface. It is considered that the amount of near-infrared rays that pass through is greater in Comparative Example 3, and the amount of near-infrared absorbed by the sheet is greater in Example 1.

[Example 4]
To the stirring mixture of the metal-insulator transition material particle-containing soft vinyl chloride resin paste of the following formulation 6, the near-infrared scattering colorant-containing vinyl ester resin stirring mixture of the following formulation 7 is 20 masses relative to the mass of the vinyl chloride resin alone. % And stirring to obtain an incompatible resin mixture liquid 4 in which the near-infrared scattering colorant-containing vinyl ester resin was uniformly dispersed. In Formulation 6, perovskite oxide (La _0.825 Sr _0.175 MnO ₃ : transition temperature 17 ° C.) particles having an average particle size of 200 nm were used as metal-insulator transition material particles, and _Formula 7 used a near-infrared scattering colorant. A Cr—Sb—Ti complex oxide (yellow: rutile type) having an average particle diameter of 600 nm was used. The following base fabric 1 is dipped in the liquid bath of the resin mixture liquid 4, pulled up, and simultaneously pressed with a mangle roll, gelled at 150 ° C. for 1 minute, heat-treated at 190 ° C. for 1 minute, and further One side was mirror-embossed. Thereby, 320 g / m ^{2 of the} incompatible resin mixture liquid 4 colored in yellow adheres to both surfaces of the base fabric 1 and is impregnated inside, and a near-infrared shielding layer having a sea-island structure is formed. A canvas-like sheet was obtained. When this near-infrared shielding layer is observed with a microscope, the near-infrared scattering colorant-containing vinyl ester resin constitutes a yellow island component, and the metal-insulator transition material particle-containing soft vinyl chloride resin constitutes a milky white sea component. It was. The average particle size of the island components in the sea-island dispersion structure was 8.5 μm. An antifouling layer coating solution of the following formulation 8 was coated on the smooth near-infrared shielding layer of the sheet that had been mirror-embossed with a gravure coater and dried at 120 ° C. for 1 minute. As a result, a yellow canvas-like heat-controllable sheet having an antifouling layer with a coating amount of 5 g / m ² formed on one side was obtained. The heat controllable sheet was subjected to various evaluations with the side on which the antifouling layer was formed as the front surface. The results are shown in Table 2.
<Formulation 6>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 100 parts by weight Di-2-ethylhexyl phthalate (plasticizer) 50 parts by weight tricresyl phosphate (plasticizer) 20 parts by weight Antimony trioxide (flame retardant) 10 parts by weight Stearic acid Zinc (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight UV absorber: benzotriazole 0.5 part by weight La _0.825 Sr _0.175 MnO _3: average particle diameter 200 nm 5 parts by weight 7>
100 parts by weight of vinyl ester resin (Trademark: Neopol 8319: Nippon Iupika Co., Ltd.)
1 part by weight of curing agent (di- (4-tert-butylcyclohexyl) peroxydicarbonate)
Cr-Sb-Ti composite oxide: 5 parts by mass of an average particle size of 600 nm <Formulation 8>
Trademark: Acryprene Pellets HBS001 (Mitsubishi Rayon Co., Ltd.) 20 parts by mass Toluene-MEK (50/50 weight ratio) (solvent) 80 parts by mass

(Base fabric 1)
Non-coarse plain woven fabric using polyester 295.3dtex (20th) short fiber spun yarn Density Warp (warp) 55 / inch Weft (weft) 48 / inch

[Example 5]
The hot-melt kneaded material of the following blend 9 containing the metal-insulator transition material particle-containing soft fluororesin is mixed with the near-infrared scattering colorant-containing soft vinyl chloride resin of the following blend 10 based on the mass of the soft fluororesin alone. 10 mass%, and heat-melt-kneading with a Banbury mixer, the near-infrared-scattering colorant containing vinyl chloride resin was disperse | distributed uniformly, and the incompatible resin mixture 5 was obtained. In _Formula 9, perovskite oxide (La _0.825 Sr _0.175 MnO ₃ : transition temperature 17 ° C.) particles having an average particle size of 200 nm were used as metal-insulator transition material particles, and near-infrared scattering colorant was used in _Formula 10 The titanium oxide particles having an average particle diameter of 1000 nm were used. This resin mixture 5 was passed through four calendar rolls set at 180 ° C. to form a near infrared ray shielding layer film 5-1 having a thickness of 0.25 mm. On the other hand, a transparent soft fluororesin hot-melt kneaded product from which the metal-insulator transition material particles are omitted from Formulation 9 is passed through four calendar rolls set at 180 ° C. to form a film 5-2 having a thickness of 0.25 mm. Molded. Next, the following base fabric 2 is inserted between the obtained film 5-1 and film 5-2, laminated by thermocompression bonding, and a tarpaulin-like white thermal controllability whose one surface is a near-infrared shielding layer. A sheet was obtained. When the near-infrared shielding layer made of film 5-1 is observed with a microscope, the near-infrared scattering colorant-containing soft vinyl chloride resin constitutes a white island component, and the metal-insulator transition material particle-containing soft fluororesin is milky white. Consists of sea components. The average particle size of the island components in the sea-island dispersion structure was 2.1 μm. About this near-infrared shielding sheet | seat, various evaluation was performed by making the side which laminated | stacked the film 5-1 into the front surface. The results are shown in Table 2.
<Formulation 9>
100 parts by mass of soft fluororesin (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin)
UV absorber: benzotriazole-based 0.5 part by mass La _0.825 Sr _0.175 MnO _3: Average particle size 200 nm 5 parts by mass

<Formulation 10>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Tricresyl phosphate (plasticizer) 50 parts by mass Cresylphenyl phosphate (plasticizer) 46 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) ) 2 parts by weight UV absorber: 0.5 parts by weight of benzotriazole series Titanium oxide: 5 parts by weight of an average particle size of 1000 nm

(Base fabric 2)
Plain woven fabric using polyester 833dtex multifilament Density Warp (warp) 19 / inch Weft (weft) 20 / inch

[Example 6]
To the heat-melt kneaded product of the soft vinyl chloride resin containing the metal-insulator transition material particles of Formulation 1 and the hot-melt kneaded product of the near-infrared scattering colorant-containing styrene butadiene block copolymer of Formula 11 below to the mass of the vinyl chloride resin alone 20 mass% was added and heat-melt-kneaded with the Banbury mixer, and the incompatible resin mixture 6 in which the near-infrared scattering colorant-containing styrene butadiene block copolymer was uniformly dispersed was obtained. As the near-infrared scattering colorant of Formulation 11, a Cr—Sb—Ti complex oxide (yellow: rutile type) having an average particle diameter of 50 nm was used. This incompatible resin mixture 6 was passed through four calender rolls set at 180 ° C. to form a near-infrared shielding layer film 6-1 having a thickness of 0.25 mm. On the other hand, a film 6-2 having a thickness of 0.25 mm was formed by passing a hot-melt kneaded product of soft vinyl chloride resin from which the metal-insulator transition material particles were omitted from formulation 1 through four calendar rolls set at 180 ° C. . Next, the base fabric 2 was inserted between the obtained film 6-1 and film 6-2 and laminated by thermocompression to obtain a tarpaulin-like sheet having one surface being a near-infrared shielding layer. When the near-infrared shielding layer composed of the film 6-1 is observed with a microscope, the near-infrared scattering colorant-containing styrene butadiene block copolymer constitutes a yellow island component, and the metal-insulator transition material particle-containing soft vinyl chloride resin is milky white. Of the sea component. The average particle size of the island components in the sea-island dispersion structure was 7.1 μm. Next, in the same manner as in Example 4, an antifouling layer was formed on the film 6-1 to obtain a heat controllable sheet. The heat controllable sheet was subjected to various evaluations with the side on which the antifouling layer was formed as the front surface. The results are shown in Table 2.

<Formulation 11>
100 parts by mass of styrene / butadiene block copolymer (product name: Asaflex 830, manufactured by Asahi Kasei Chemicals Corporation)
Cr—Sb—Ti composite oxide: average particle size 50 nm 10 parts by mass

[Example 7]
The following base fabric 3 is immersed in a liquid bath of the following formulation 12, pulled up and simultaneously pressed with a mangle roll, gelled at 150 ° C. for 1 minute, and then heat treated at 190 ° C. for 1 minute. Resin was adhered to 70 g / m ² to form an adhesive resin layer. Next, the hot-melt kneaded product of the blended metal-insulator transition material particle-containing soft vinyl chloride resin and the near-infrared scattering colorant-containing styrene butadiene block copolymer of the following formula 13 are mixed with the vinyl chloride resin alone. 20 mass% was added to the mass, and it was heat-melt-kneaded with a Banbury mixer to obtain an incompatible resin mixture 7 in which the near-infrared scattering colorant-containing styrene butadiene block copolymer was uniformly dispersed. A Co—Al composite oxide (blue: spinel type) having an average particle diameter of 50 nm was used as the near-infrared scattering colorant of Formulation 13. This incompatible resin mixture 7 was passed through four calender rolls set at 180 ° C. to form two near infrared shielding layer films 7 having a thickness of 0.15 mm. Next, the base fabric 3 having an adhesive resin layer formed between the two obtained films 7 was inserted and laminated by thermocompression to obtain a sheet containing a glass base fabric having a near-infrared shielding layer on both sides. . When the near-infrared shielding layer made of the film 7 is observed with a microscope, the near-infrared scattering colorant-containing styrene butadiene block copolymer constitutes a blue island component, and the metal-insulator transition material particle-containing soft vinyl chloride resin is milky white sea. Consists of ingredients. The average particle size of the island components in the sea-island dispersion structure was 7.1 μm. Subsequently, the composition liquid of the following mixing | blending 14 was apply | coated with the gravure coater, it dried for 1 minute at 120 degreeC, and it cooled, and formed the resin intermediate | middle layer of 5 g / m < ² > on both surfaces. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 14 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, Thereby, a total of 10 g / m ² of additive migration preventing layers composed of a resin intermediate layer and an additional resin layer were formed on both surfaces. Next, a coating solution for forming an adhesion / protection layer having the following formulation 15 was applied on the additive migration preventing layer on one surface with a gravure coater, dried at 100 ° C. for 1 minute, cooled, and 1.5 g / m ^2. Further, an antifouling layer-forming coating solution of the following formulation 16 was applied on the adhesion / protective layer with a gravure coater, dried at 120 ° C. for 2 minutes, cooled and 1.5 g / A heat-controllable sheet on which an antifouling layer containing a photocatalytic substance of m ² was formed was obtained. The heat controllable sheet was subjected to various evaluations with the side on which the photocatalytic substance-containing antifouling layer was formed as the front surface. The results are shown in Table 2.
<Formulation 12>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 100 parts by weight Di-2-ethylhexyl phthalate (plasticizer) 50 parts by weight Thermally crosslinkable adhesive 10 parts by weight Antimony trioxide (flame retardant) 10 parts by weight Epoxidized soybean oil ( Stabilizer) 4 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight UV absorber: benzotriazole 0.5 part by weight Toluene (solvent) 20 parts by weight

<Formulation 13>
100 parts by mass of styrene / butadiene block copolymer (product name: Asaflex 830, manufactured by Asahi Kasei Chemicals Corporation)
Co-Al composite oxide: average particle size 50 nm 10 parts by mass

<Formulation 14>
20 parts by mass of vinylidene fluoride-tetrafluoroethylene copolymer resin (Trademark: Kyner 7201: Elf Atchem Japan Co., Ltd.)
Silica: (Trademark: NipSeal E-75: Tosoh Silica Co., Ltd.) 5 parts by mass MEK (solvent) 80 parts by mass

<Formulation 15>
Ethanol-ethyl acetate (50/50 mass ratio) solution containing 8 mass% (solid content) of acrylic silicon resin having a silicon content of 3 mol% 100 mass parts 20% ethanol solution of methyl silicate MS51 (Colcoat Co., Ltd.) Siloxane) 8 parts by mass γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by mass

<Formulation 16>
Water-ethanol (50/50 mass ratio) solution in which a nitric acid acidic titanium oxide sol corresponding to a titanium oxide content of 10% by mass is dispersed 50 parts by mass Water in which a nitric acid acidic silica sol corresponding to a silicon oxide content of 10% by mass is dispersed -50 parts by mass of ethanol (50/50 mass ratio) solution

(Base fabric 3)
Plain woven fabric using glass fiber with filament diameter 9μm / 75tex Density Warp (warp) 40 / inch Weft (weft) 30 / inch Scouring (heat cleaning)
Silane coupling treatment Methacryloxypropyltrimethoxysilane (Toray Dow Corning Z6030)

  The heat-controllable sheets of Examples 4 to 7 have a near-infrared shielding layer having a sea-island dispersion structure composed of a mixture of a synthetic resin containing metal-insulator transition material particles and a synthetic resin containing a near-infrared scattering colorant. Each of them was a sheet excellent in heat shielding, temperature rising / falling at low temperature, and daylighting. In addition, because it is a laminated body including fiber base fabric, membrane structures such as tent warehouses, large event tents, awning tents, awning monuments, decorative tents, blinds, seat shutters, partitions and truck hoods that require high strength are required. It is a heat-controllable sheet suitable for constituting. Examples 4, 6, and 7 each have an antifouling layer, and since Example 5 is a soft fluororesin, the sea component is excellent in antifouling properties. A decrease in daylighting due to the adhesion of dirt is prevented, and the beauty is maintained. Further, by preventing the adhesion of dirt, the sheet had a gentle temperature drop at low temperatures even after 1 year exposure, and maintained heat storage for a long time.

[Comparative Example 4]
A milky white canvas-like sheet having a mirror embossed surface on one side was obtained in the same manner as in Example 4 except that the near-infrared scattering colorant was omitted from Formulation 7 and the antifouling layer was not provided. When the both sides of the base fabric 1 and the resin layer impregnated therein are observed with a microscope, a transparent vinyl ester resin constitutes an island component, and a soft vinyl chloride resin containing metal-insulator transition material particles constitutes a milky white sea component. It was. The average particle size of the island components in the sea-island dispersion structure was 8.5 μm. The sheet was subjected to various evaluations with the side subjected to mirror embossing as the front surface. The results are shown in Table 3.

  In the sheet of Comparative Example 4, the resin layer adhered to both surfaces of the base fabric 1 and the resin layer impregnated therein has a sea-island structure, and the sea component contains metal-insulator transition material particles, but the island component is near-infrared. Since it did not contain a scattering colorant, it was a sheet inferior in the near-infrared shielding property but inferior to the initial heat shielding property, although it had higher daylighting performance than Example 4. Although the heat-shielding property is slightly improved after 1 year exposure, the sheet of Comparative Example 4 does not have an antifouling layer, and dirt adhered to the surface absorbs near-infrared rays and shields it. This is probably because the sea component containing the metal-insulator transition material radiated energy as far infrared rays. Further, regarding the temperature rise and temperature drop at low temperatures, both are inferior to Example 4 in the initial stage, and after one year exposure, the temperature rise is about the same as Example 4, and the temperature drop is further inferior to that in Comparative Example 4. It was. Again, it can be considered that the dirt adhering to the surface absorbed near infrared rays emitted from the lamp to increase the temperature, and after the lamp was extinguished, the dirt emitted far infrared rays, so that the temperature decrease was accelerated.

[Comparative Example 5]
The heat-melt kneaded material of the styrene butadiene block copolymer containing the near-infrared scattering colorant of the compound 11 is added to the heat-melt kneaded material of the soft vinyl chloride resin from which the metal-insulator transition material particles are omitted from the compound 1, and the mass of the vinyl chloride resin alone. 20 mass% was added, and it heat-kneaded and kneaded with the Banbury mixer, and obtained the incompatible resin mixture ratio -5 which disperse | distributed the near-infrared-scattering coloring agent containing styrene butadiene block copolymer uniformly. This incompatible resin mixture ratio -5 was passed through four calender rolls set at 180 ° C. to form a film ratio 5-1 having a thickness of 0.25 mm. On the other hand, hot melt kneaded material of soft vinyl chloride resin from which the metal-insulator transition material particles are omitted from formulation 1 is passed through four calender rolls set at 180 ° C. to form a film ratio 5-2 with a thickness of 0.25 mm. did. Next, the base fabric 2 was inserted between the obtained film ratio 5-1 and film ratio 5-2, and laminated by thermocompression to obtain a tarpaulin-like sheet. When a layer having a film ratio of 5-1 was observed with a microscope, the near-infrared scattering colorant-containing styrene butadiene block copolymer constituted a yellow island component, and the soft vinyl chloride resin constituted a sea component. The average particle size of the island components in the sea-island dispersion structure was 7.1 μm. About this sheet | seat, various evaluation was performed by making the side which laminated | stacked film ratio 5-1 into the front surface. The results are shown in Table 3.

  The sheet of Comparative Example 5 has a resin layer with a sea-island structure, and the island component contains a near-infrared scattering colorant, but the sea component does not contain metal-insulator transition material particles, so that the light-collecting property and the shielding property are not affected. The sheet was inferior in temperature rise at low temperatures, although it was excellent in heat. Although the heat-shielding property is reduced after exposure for one year, it is considered that the sheet of Comparative Example 5 does not have an antifouling layer, and the reflection of near infrared rays is reduced due to the adhesion of dirt to the surface. .

  The heat-controllable sheet of the present invention prevents excessive temperature rise of the sheet by radiating thermal energy as far-infrared rays under hot weather in summer, and shields near-infrared rays to show high heat-shielding properties. At low temperatures, there is little radiation of heat heated by sunlight, heating, etc., and it has heat storage properties, and it has daylighting and coloring freedom, so it is a tent warehouse, event tent, disaster tent, agriculture and horticulture It can be suitably used for a membrane structure such as a house, a truck hood, a flexible container, a awning tent, a awning monument, a decorative tent, a blind, a sheet shutter, or a partition. Moreover, the heat-controllable sheet containing a flexible solar cell module can be beneficially used as a sheet-like solar cell with stable output.

1: Thermally controllable sheet 2: Near-infrared shielding layer having sea-island structure 3: Island component 3-1: Island component containing near-infrared scattering colorant 3-2: Island component containing metal-insulator transition material particles 4: Sea component 4-1: Sea component containing near-infrared scattering colorant 4-2: Sea component containing metal-insulator transition material particles 5: Fiber base fabric 6: Resin having no sea-island structure Layer 7: Flexible solar cell module 8: Antifouling layer 9: Surface temperature sensor 10: Styrofoam plate 11: Sample for measurement 12: Halogen lamp

Claims (7)

  A flexible sheet comprising a near-infrared shielding layer, wherein the near-infrared shielding layer comprises a mixture of a synthetic resin containing metal-insulator transition material particles and a synthetic resin containing a near-infrared scattering colorant. A heat-controllable sheet, which is an incompatible resin layer formed by a dispersion structure.   The heat-controllable sheet according to claim 1, wherein in the sea-island dispersion structure, a sea component includes the metal-insulator transition material particles, and an island component includes the near-infrared scattering colorant.   The heat-controllable sheet according to claim 1, wherein in the sea-island dispersion structure, a sea component includes the near-infrared scattering colorant, and an island component includes the metal-insulator transition material particles.   The metal-insulator transition material particles include one or more selected from metal composite oxide particles having a perovskite structure and containing manganese, and metal composite oxide particles having a corundum structure and containing chromium and vanadium, The heat-controllable sheet according to any one of claims 1 to 3, which has a transition temperature in a range of 10 to 60 ° C.   The near infrared scattering colorant is titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, chromium oxide, iron oxide, tin-doped indium oxide, indium-doped tin oxide, antimony. A metal oxide selected from doped tin oxide, and a rutile, hematite, or spinel structure, titanium, zinc, antimony, iron, nickel, cobalt, chromium, magnesium, copper, manganese, aluminum, The heat-controllable sheet according to any one of claims 1 to 3, comprising at least one selected from niobium and a metal composite oxide containing at least two components of silicon.   The heat-controllable sheet according to any one of claims 1 to 5, wherein the flexible sheet is a laminate including a fiber base fabric.   The heat-controllable sheet according to any one of claims 1 to 6, wherein a flexible solar cell module is laminated on the outermost surface of the flexible sheet.