JP2011052357A - Heat-insulating lighting film material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lighting film material having light transmission properties, a high freedom of hue such as transparency, colored transparency, colored translucency and colored opacity, and excellent heat-insulation effect. <P>SOLUTION: The heat-insulating lighting film material (1) is a flexible film material including a fiber base cloth (2) and a flexible resin coating layer (3) formed on at least one surface of the cloth and has a light transmittance (measured by JIS Z8722.5.4 (condition g)) of 3-70%, wherein at least one layer of the flexible resin coating layer has a sea-island structure comprising an incompatible mixture formed by synthetic resin blend, and either one of the sea component (4) and the island component (5) of the sea-island structure contains a thermally controllable coloring agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a daylighting film material having a heat shielding property. More specifically, the present invention is light transmissive, transparent, colored transparent, colored translucent, colored opaque, etc., has a high degree of freedom of hue surface, and has excellent heat shielding properties, in particular, a sun tent, The present invention relates to a heat-shielding daylighting film material and a method for producing the same, which are preferably used for sunshade monuments, decorative tents, tent warehouses, event tents, truck hoods, blinds, partitions, sheet shutters, agricultural and horticultural sheets, and the like.

  A film material in which a flexible resin is coated on a fiber base fabric by a coating method, a dipping method, a calendar method, a T-die extrusion method, or the like is easy to assemble and install, and has a high degree of freedom in design such as hue and structure. Because of its high price, it is used in a wide range of fields such as awning tents, awning monuments, decorative tents, tent warehouses, event tents, truck hoods, and blinds. However, the conventional film material is highly transmissive or absorbing near infrared rays contained in solar radiation, so that the infrared light transmitted or absorbed from the surface side of the film material directly warms the space on the back side of the film material. The absorbed infrared rays are also emitted from the back side of the film material as radiant heat by raising the temperature of the film material. For this reason, for example, when the above-mentioned film material is used in a tent warehouse, the internal temperature becomes extremely high under the strong sunlight in summer, so that it is difficult for humans to work for a long time, and it is also possible to use the awning tent. When it is used for the above, it has the effect of preventing glare and reducing ultraviolet rays, but the fact is that the cooling effect is hardly recognized. In the case of a tent warehouse, it is possible to lower the internal temperature by using cooling as in a normal building, but the cooling efficiency is very low, and considering the energy costs and the environmental burden associated with it, A tent warehouse was not preferred in practice.

  For the above problem, when using a white film material, for example, a film material in which a white pigment such as titanium oxide is kneaded in a flexible resin layer, infrared rays contained in solar radiation are scattered, and heat shielding properties are exhibited. It is known. In practical use of such a white film material, it is possible to obtain heat shielding properties at low cost because no special auxiliary processing is required, but by requiring a large amount of white pigment, the light transmittance decreases, for example Inside the tent warehouse using such a film material, there was a problem that lighting was necessary even during the day. As another heat-shielding film material, a method of kneading metal powder into a flexible resin layer (for example, see Patent Documents 1 and 2) is also performed. Similarly, the daylighting and the degree of freedom in hue selection were low. In addition, as a heat shielding technique using a pigment, for example, a chromatic and black composite pigment obtained by coating a white pigment with a near-infrared reflective and / or near-infrared transparent pigment (see, for example, Patent Document 3) is known. . This pigment is a white pigment that reflects near-infrared, and is coated with an organic dye that does not absorb near-infrared, so that both coloring in the visible light region and reflection in the near-infrared region are achieved. It is. According to this, the hue of the film material can be freely selected to some extent, and the desired heat shielding property can also be obtained. However, if these pigments are kneaded as they are into the flexible resin coating layer of the film material, a white pigment can be obtained. Since the light shielding property is large as in the case of using a light source, there is a problem that a desired lighting property cannot be obtained. In addition, a white pigment having an average particle diameter of 300 nm to 2000 nm and a refractive index of 1.3 to 3.0, an organic infrared reflective pigment, or an oxide of an element such as Si, Zr, Mg, Ca, Fe, Mn, A thermal barrier coating containing a thermal barrier pigment coated with a double oxide, carbide, nitride, or the like has also been proposed (see, for example, Patent Document 4). The pigment contained in this thermal barrier paint has a particle diameter of 300 nm to 2000 nm, so that the scattering of visible light is reduced and the near infrared ray is effectively scattered. When used in the paint, the pigment is not affected much. Heat resistance is obtained, but heat shielding properties are insufficient when added in a small amount, and since light shielding properties increase when added in large amounts, both heat shielding properties and daylighting properties are obtained when used for film materials such as tents. It was difficult.

  In order to improve heat insulation, it is also known to provide a foam layer in the structure of the film material. Such a film material is capable of absorbing near-infrared rays contained in solar radiation, and the film material on its surface. The foam layer prevents the heat on the surface side of the film material that has been absorbed by the side from rising to the back side. In this case, if infrared rays are transmitted, a sufficient heat shielding effect cannot be obtained. Therefore, in order to increase the heat shielding effect, a large amount of pigment, filler, etc. is added to the film material, or There is a problem that it is necessary to increase the thickness of the foamed layer. In addition, a method of partially compressing the foam layer and increasing translucency at the compressed portion has also been proposed (see, for example, Patent Document 5). There is a problem that the effect is reduced, and if the amount is small, the translucency is insufficient. Furthermore, since the film material having a foam layer is thick, the film material is not easy to handle, and the mechanical strength is insufficient. Therefore, the film material is unsuitable for a film structure such as a tent. The application of infrared reflectivity of metal thin films and metal oxide thin films has also been studied. For example, by transferring a metal foil to a coarse knitted fabric, the metal solid portion (the yarn portion of the coarse knitted fabric) and By providing a metal-deficient part (open area of the coarse knitted fabric), applying a transparent film layer to the metal transfer side of this coarse knitted fabric, and forming a base sheet on the opposite side, both heat shielding effect and lighting effect Is known to increase (see, for example, Patent Document 6). In the film material having this configuration, it is possible to set the hue to some extent by coloring the transparent film layer and / or the base sheet. However, on the side where the metal is transferred, the color tone having high glossiness with metallic luster is obtained. However, there is a problem that the degree of freedom of hue is insufficient, and in addition, the weather resistance is insufficient. As other thermal barrier film materials, metal oxide thin films such as indium / tin oxide (ITO) and antimony / tin oxide (ATO), metal thin films, or metal thin films can be made of a transparent high refractive index material by vacuum deposition or sputtering. A transparent heat-shielding thin film (see, for example, Patent Documents 7 to 9) having a heat-shielding layer sandwiched between thin films is known, and this heat-shielding layer has a function of transmitting visible light and reflecting infrared light. Therefore, if these are formed on the surface of the film material, the hue of the film material can be freely selected, and it is possible to impart heat shielding properties without significantly affecting the visible light transmittance. Further, a light-collecting heat shielding film material (for example, see Patent Document 10) in which a metal thin film or metal oxide thin film and a flexible resin layer containing fine particles of metal oxide or a near-infrared absorbing dye are combined has also been proposed. Therefore, according to this configuration, an effect that combines the respective heat shielding properties is expected. However, the formation of a thermal barrier layer using vacuum deposition or sputtering requires a large-scale decompression facility, so that it is not very versatile, and it is applied to the thick film material containing a large amount of plasticizers and additives. Technical application of including a thermal layer was difficult. Therefore, up to now, a film material for a practical tent structure having both a heat shielding effect and a daylighting property and having a high degree of coloring freedom has not yet been provided.

JP-A-8-49171 JP-A-6-146166 JP 2002-249676 A JP-A-2005-97462 Japanese Patent Publication No.57-55066 Japanese Patent Publication No. 4-60428 Japanese Patent Laid-Open No. 51-66841 Japanese Patent Publication No. 63-5263 Japanese Examined Patent Publication No. 6-28938 JP 2003-251728 A

  The present invention solves the above-mentioned problems of the prior art, has a high degree of freedom in hue, transparent, colored transparent, colored translucent, colored opaque, etc., has translucency, and has excellent near-infrared shielding properties. In particular, we provide daylighting film materials with excellent heat-shielding properties that are suitable for use in awning tents, awning monuments, decorative tents, tent warehouses, event tents, truck hoods, blinds, partitions, sheet shutters, agricultural and horticultural sheets, etc. It is something to try.

  In order to solve the above problems, the present inventor has made a sea-island structure in which at least one flexible resin coating layer is composed of an incompatible mixture of a synthetic resin blend as a result of intensive studies. It has been found that a film material having light transmittance, a high degree of freedom in hue, and excellent heat shielding properties can be obtained by including one of the sea component and the island component with a heat-controllable colorant. The invention has been completed.

  That is, the heat insulating daylighting film material of the present invention includes a fiber base fabric and a flexible resin coating layer formed on at least one surface thereof, and has a light transmittance (measured according to JIS Z8722.5.4 (condition g)) of 3. -70% flexible membrane material, wherein at least one of the flexible resin coating layers has a sea-island structure made of an incompatible mixture of a synthetic resin blend, and in the sea-island structure, Alternatively, either one of the island components contains a heat-controllable colorant. In the sea-island structure, the heat-shielding daylighting film material of the present invention has a difference between the refractive index of the synthetic resin constituting the sea component and the refractive index of the synthetic resin constituting the island component, and the refractive index difference is 0.05. The average particle size of the island component dispersed in the sea component is preferably 0.5 to 20.0 μm. The heat-shielding daylighting film material of the present invention preferably contains at least one selected from metal oxide fine particles, metal composite oxide fine particles, and near-infrared absorbing materials as the heat-controllable colorant. In the heat-shielding daylighting film material of the present invention, the metal oxide fine particles are titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, chromium oxide, iron oxide, tin-doped indium oxide, indium. It is preferable that it is 1 or more types chosen from dope tin oxide and antimony dope tin oxide. In the heat-shielding daylighting film material of the present invention, the metal composite oxide fine particles include two or more of titanium, zinc, antimony, iron, nickel, cobalt, chromium, magnesium, copper, manganese, aluminum, niobium, and silicon. It is preferable that it is 1 or more types selected from the metal complex oxide containing a component. In the heat-shielding daylighting film material of the present invention, the near-infrared absorbing material is selected from phthalocyanine compounds, naphtholquinone compounds, imonium compounds, anthraquinone compounds, aminium compounds, and nickel-thiol complex compounds. One or more are preferable. The heat-shielding daylighting film material of the present invention is provided with an antifouling layer on the flexible resin coating layer, and the glossiness after 1000 hours (JIS K7105) according to the sunshine weatherometer weathering accelerated test (JIS K7350-4). .5.2) The retention is preferably 80 to 100%. The heat-shielding daylighting film material of the present invention has an antifouling layer provided on the flexible resin coating layer, and a color difference ΔE (JIS K7105.5.4) between outdoor exposure and after one year is 0.1-5. 0.0 is preferred. In the heat shielding daylighting film material of the present invention, the antifouling layer preferably contains a photocatalytic substance. The method for producing a heat-shielding daylighting film material of the present invention includes a fiber base fabric and a flexible resin coating layer having a sea-island structure in which either a sea component or an island component contains a heat-controllable colorant. In the thermal daylighting film material, the sea-island structure is constituted by a synthetic resin incompatible couple, and one of the synthetic resin incompatible couple is used as a thermal control colorant-containing synthetic resin. It is preferable that the average particle diameter of the island component dispersed in the sea component is 0.5 to 20.0 μm by mixing with the other synthetic resin forming the synthetic resin incompatible pair. The method for producing a heat-shielding daylighting film material of the present invention has a difference between the refractive index of the synthetic resin constituting the sea component and the refractive index of the synthetic resin constituting the island component in the sea-island structure, and the refractive index difference is It is preferable that it is 0.05 or more. In the method for producing a heat-shielding daylighting film material according to the present invention, the heat-controllable colorant preferably contains one or more selected from metal oxide fine particles, metal composite oxide fine particles, and near-infrared absorbing materials. . In the method for producing a heat-shielding daylighting film material of the present invention, the metal oxide fine particles include titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, chromium oxide, iron oxide, tin-doped oxide. It is preferable to include at least one selected from indium, indium-doped tin oxide, and antimony-doped tin oxide. In the method for producing a heat-shielding daylighting film material of the present invention, the metal composite oxide fine particles are selected from the group consisting of titanium, zinc, antimony, iron, nickel, cobalt, chromium, magnesium, copper, manganese, aluminum, niobium, and silicon. It is preferable to include at least one selected from metal complex oxides including at least one component. In the method for producing a heat-shielding daylighting film material of the present invention, the near-infrared absorbing substance is composed of a phthalocyanine compound, a naphtholquinone compound, an imonium compound, an anthraquinone compound, an aminium compound, and a nickel-thiol complex compound. It is preferable to include at least one selected.

  According to the present invention, there is a need for a special production facility for a daylighting film material having light transmittance, high transparency in hue, such as transparent, colored transparent, colored translucent, and colored opaque, and having excellent heat shielding properties. Instead, it can be manufactured and provided with high productivity. Since the heat-shielding daylighting film material of the present invention has an effect of transmitting visible light and shielding infrared rays, it is possible to provide a bright and cool environment, and in particular, a awning tent, a awning monument, a decorative tent, and a tent warehouse. It can be suitably used for event tents, truck hoods, blinds, partitions, sheet shutters, agricultural and horticultural sheets, and the like.

The figure which shows an example of the heat-shielding daylighting film material of the present invention, and shows a state where the thermoplastic resin coating layer has a sea-island structure and the island component contains a heat-controllable colorant. The figure which shows an example of the heat-shielding daylighting film material of the present invention, and shows a state where the thermoplastic resin coating layer has a sea-island structure and the sea component contains a heat-controllable colorant.

  The heat-shielding daylighting film material of the present invention is a flexible film material having a fiber base fabric and a flexible resin coating layer formed on at least one surface thereof. At least one layer has a sea-island structure composed of an incompatible mixture of a synthetic resin blend, and in the sea-island structure, either the sea component or the island component contains a heat-controllable colorant. The method for producing a heat-shielding daylighting film material of the present invention includes a fiber base fabric and a flexible resin coating layer having a sea-island structure in which either a sea component or an island component contains a heat-controllable colorant. In the heat-shielding daylighting film material comprising, the sea-island structure is constituted by a synthetic resin incompatible couple, and one of the synthetic resin incompatible couple is used as a heat-controllable colorant-containing synthetic resin, and the heat-controllable colorant is contained. A synthetic resin is mixed with the other synthetic resin forming the synthetic resin incompatible pair so that the average particle size of the island component dispersed in the sea component is 0.5 to 20.0 μm. is there.

  The form of the heat insulating daylighting film material of the present invention is tarpaulin, a waterproof film material such as canvas, or a mesh sheet. Among them, canvas and mesh sheets are dispersions in which a flexible resin solubilized in an organic solvent, a flexible resin emulsion (latex) emulsion-polymerized in water, or a dispersion in which the flexible resin is forcibly dispersed in water. It can be manufactured by dipping using a water-dispersed resin such as resin, soft polyvinyl chloride resin paste sol, etc. (double-sided processing on fiber fabric), coating processing (single-sided processing or double-sided processing on fiber fabric), etc. it can. Tarpaulin is a method in which a film or sheet molded by a calendar molding method or a T-die extrusion method is laminated with an adhesive layer on one or both sides of a fiber base fabric, or through a void space on both sides of a fiber fabric. It is preferable to manufacture by a method of heat laminating and laminating, and further, it can be carried out by a combination of dipping processing or coating processing and film lamination. In the case of the daylighting membrane material of the present invention, opaque colored or transparent colored tarpaulin, and canvas, the light transmittance (JIS Z8722.5.4 (condition g)) is 3 to 35%, and mesh sheet and transparent tarpaulin is 10 to 70%. It is preferable that

  In the present invention, the flexible resin coating 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 (PE, PP, etc.), olefin copolymer resins, urethane resins, 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, polyester amide, polyphenylene sulfide, polyether ester, vinyl ester resin, unsaturated polyester resin, etc. Some thermoplastics and curable resins That.

  In the present invention, at least one flexible resin coating layer has a sea-island structure composed of an incompatible mixture of a synthetic resin blend, and the combination of the synthetic resin blends is not particularly limited as long as it is incompatible. Examples of 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, polystyrene and polyethylene, polystyrene and polypropylene, urethane resin and polyethylene, urethane resin and polypropylene, polyester resin and polyethylene, polyester resin and polypropylene, polyamide and polycarbonate, acrylic resin and polystyrene A blend of two types of synthetic resins such as acrylic resin and polycarbonate, polyamide and styrene resin, and polyamide and polypropylene is preferable. Another kind of flexible resin can be further contained with respect to these incompatible flexible resin pairs.

  These incompatible mixtures are preferably sea-island structures with a cloudy appearance showing a phase separation structure. In this sea-island 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 determined by setting the ratio of synthetic resin A and synthetic resin B. It 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. 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. The island component content with respect to the entire flexible resin coating layer having a sea-island structure is preferably 2.9 to 33.3% by volume, and more preferably 4.7 to 28.6% by volume. Further, 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 C in the sea-island structure. The island component may be composed of the island component of the flexible resin A and the island component of the flexible resin C. In the present invention, the thickness of the flexible resin coating layer having a sea-island structure is 0.05 to 1.0 mm, preferably 0.1 to 0.5 mm.

  In the flexible resin coating layer having the sea-island structure of the present invention, either the sea component or the island component is colored with a heat-controllable colorant. In order to form a flexible resin coating layer colored with either a sea component or an island component, for example, a sol, a solution, a dispersion, an uncured solution containing two types of synthetic resins constituting an incompatible mixture Any one of the resin mixed solutions such as the above was colored in advance, and the colored resin mixed solution and the non-colored resin mixed solution were mixed and stirred to prepare an average particle size of the island component to 0.5 to 20.0 μm. A method of coating the incompatible resin mixture liquid on the fiber base fabric by dipping or coating, or by coloring one of the two types of synthetic resins constituting the incompatible mixture in advance, And a colored synthetic resin are melt-mixed and an incompatible resin mixture prepared with an average particle size of 0.5 to 20.0 μm is formed into a film or sheet by a calendar molding method or a T-die extrusion method. In addition, a method of laminating the fiber base fabric can be adopted. By these methods, it is possible to obtain a flexible resin coating layer composed of a colored sea component and a non-colored island component or a structure composed of a non-colored sea component and a colored island component. In the mixture of the present invention, the colored synthetic resin component does not mix with the non-compatible non-colored synthetic resin component, so the non-colored synthetic resin component is not colored by the colorant contained in the colored synthetic resin component. . In the present invention, the sea-island structure may be colored with a different colorant between the sea component and the island component. At least one colorant that colors the sea component or the island component has thermal controllability. Further, in the daylighting film material of the present invention, the flexible resin coating layer has light transmittance as compared with the case where the entire coating layer is colored because either the sea component or the island component is colored. At the same time, good heat shielding properties can be secured. In the daylighting film material of the present invention, it is preferable that the flexible resin coating layer has an island component colored.

  In the flexible resin coating layer having the sea-island structure of the present invention, if light 380 to 780 nm in the visible light region is not scattered so much and more infrared rays exceeding 780 nm can be scattered, the light transmittance is improved and the light shielding is performed. The effect of improving thermal properties can be expected. In order to obtain such an effect, it is preferable that the average particle diameter of the island component is 0.5 to 20 μm and the difference in refractive index between the sea component and the island component is 0.05 or more. Due to the difference in the refractive index between the sea component and the island component, light is scattered by the refractive scattering phenomenon at the interface. The refractive index of the sea component and the island component may be higher on either side, but the island component preferably has a higher refractive index than the sea component. If the difference in refractive index between the sea component and the island component is less than 0.05, the refractive scattering phenomenon at the interface does not sufficiently occur, and a sufficient infrared scattering effect cannot be obtained, and the heat shielding property may not be improved. The preferred average particle size of the island component varies depending on the difference in refractive index between the sea component and the island component. For example, if the refractive index difference is 0.05, the average particle size of the island component is preferably 5 to 19 μm. If the rate difference is 0.2, the average particle size of the island components is preferably 1 to 5 μm. If the average particle size of the island component is less than 0.5 μm, the light scattering increases in part of the visible light region due to the refraction and scattering phenomenon at the interface, and the light transmittance decreases or the light in the visible region is partially The flexible resin coating layer may appear to be colored due to scattering. When the average particle diameter of the island component exceeds 20 μm, scattering over the entire visible light region may occur, and the light transmittance may be lowered. The shape of the island component is a sphere, a distorted sphere, a meteorite shape, a rugby ball shape, or the like. The refractive index can be obtained by an Abbe refractometer using the D line as a light source. Moreover, the average particle diameter of an island component is calculated | required by measuring and averaging the diameter of the island component distributed in a fixed area from a microscope enlarged photograph.

  The heat-controllable colorant used for coloring the sea component or island component of the present invention contains at least one selected from metal oxide fine particles, metal composite oxide fine particles, and near-infrared absorbing materials. Is effective to obtain.

  The metal oxide fine particles used in the present invention are not particularly limited as long as they are particles made of a metal oxide that reflects infrared rays. Titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, manganese oxide, barium oxide, tin oxide , Zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, 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 antimony-doped tin oxide, etc., among which titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, chromium oxide, iron oxide, tin-doped indium oxide, indium-doped tin oxide, and the like Antimony-doped tin oxide is preferably used. These metal oxide fine particles may be used alone or in combination of two or more. In addition, among these substances, particularly for substances exhibiting photocatalytic activity such as titanium oxide, zinc oxide, and tungsten oxide, the surface is coated with, for example, silicon dioxide (silica) or aluminum oxide (alumina) to suppress the photocatalytic activity. May be. There is no restriction | limiting in particular in the particle diameter of metal oxide microparticles | fine-particles, It can select suitably from the normally available particle | grains of the average particle diameter of 1-10000 nm, and a particle | grain with an average particle diameter of 20-5000 nm is used more preferable. In particular, in order to increase the transmittance of visible light to obtain a high light transmittance and to selectively scatter near infrared rays to obtain a high heat shielding property, the average particle diameter depends on the refractive index of the metal oxide fine particles. Particles having an average particle diameter of 20 to 100 nm are preferably used in order to obtain a flexible resin layer having high light transmittance and transparency. The metal oxide fine particles contained in the sea component and the island component are 0.1 to 30% by mass, preferably 0.5 to 10% by mass with respect to the synthetic resin constituting the sea component or the island component. When the addition amount is less than 0.1% by mass, the infrared reflection effect is insufficient, and sufficient heat shielding properties may not be obtained. On the other hand, if the addition amount exceeds 30 parts by mass, the light transmittance may be lowered, and sufficient lighting properties may not be obtained.

  The metal composite oxide fine particles used in the present invention 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 inorganic color pigments containing two or more components of silicon (Si) can be used. As long as it contains two or more of these, metal composite oxide fine particles further containing components other than those described above can 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, Ni-W, Ni-W-Ti, Fe-W-Ti, Fe-Zn-Ti, Fe- l-Ti, Fe-Ti, Fe-Mo, Cr-Sb, Cr-Sb-Ti, Mn-Sb-Ti, Ti-Sb-Ni, Cr-Sn, Fe-Co-Mn-Ni, Ti-Sb- Complex oxides composed of components such as Cr and Zr—Fe can be exemplified, and among these, particles having a desired hue can be used alone or in combination of two or more. In particular, Co—Al, Co—Al—Cr, Co—Zn—Ni—Ti, Co—Zn—Cr—Ti, Co—Cr—Mg—Zn—Al, Co—Fe—Cr, Cr—Fe, Cr— Metal composite oxides composed of Fe-Zn-Ti, Fe-Zn-Ti, Fe-Al-Ti, Cr-Sb-Ti, Mn-Sb-Ti, and Ti-Sb-Ni components are infrared reflective. It is excellent and can be preferably used in the present invention. There is no restriction | limiting in particular in the particle diameter of metal complex oxide microparticles | fine-particles, It can select suitably from a particle | grain with an average particle diameter of 1-10000 nm, and a particle | grain with an average particle diameter of 20-5000 nm is used more preferable. In particular, particles having an average particle diameter of 350 to 2000 nm are preferable in order to increase the transmittance of visible light and obtain a high light transmittance as well as a heat shielding property, and also increase the light transmittance and have flexibility with transparency. In order to obtain a resin layer, particles having an average particle diameter of 20 to 100 nm are preferably used. The metal composite oxide fine particles contained in the sea component and the island component are 0.05 to 30% by mass, preferably 0.5 to 10% by mass with respect to the synthetic resin constituting the sea component or the island component. If the amount of the metal composite oxide fine particles added is less than 0.05% by mass, coloring may be insufficient. On the other hand, if the addition amount exceeds 30 parts by mass, the light transmittance may be lowered, and sufficient lighting properties may not be obtained.

  As the near infrared ray absorbing substance used in the present invention, for example, phthalocyanine compounds, naphtholquinone compounds, imonium compounds, anthraquinone compounds, aluminum compounds, nickel-thiol complex compounds, and the like can be used. These are disclosed in JP 51-135886, JP 56-143242, JP 58-13676, JP 60-23451, JP 61-115958, JP 63-295578, JP-A-4-174402, JP-A-5-93160, JP-A-5-222302, JP-A-6-264050, etc. Can be used. The near infrared ray absorbing substance contained in the sea component and the island component is preferably 0.01 to 3.0% by mass, particularly preferably 0.1 to 1.0% by mass with respect to the synthetic resin constituting the sea component or the island component. %. When the addition amount is less than 0.01% by mass, the infrared absorption effect is insufficient and sufficient heat shielding properties may not be obtained. On the other hand, if the amount added exceeds 3.0 parts by mass, the light transmittance may be reduced, and sufficient lighting properties may not be obtained.

  In the daylighting film material of the present invention, the flexible resin coating layer may contain other known additives as necessary. Examples of the additive include an antistatic agent, a flame retardant, a plasticizer, a flexibility imparting agent, a filler, an adhesive, a crosslinking agent, an ultraviolet absorber, an antioxidant, a stabilizer, a lubricant, a processing aid, and a leveling. Agents, antifoaming agents, antibacterial agents, antifungal agents, fluorescent whitening agents, fluorescent pigments, organic pigments, phosphorescent pigments and the like.

  In the daylighting film material of the present invention, in order to prevent the heat-shielding effect due to the adhesion of dirt over time and the decrease in light transmittance, and to maintain the aesthetic appearance, at least one layer of anti-reflection coating is provided on the flexible resin coating layer. A dirty layer is preferably provided. The antifouling layer is not particularly limited in its formation method and material as long as it does not impair the heat shielding property and light transmittance of the daylighting film material 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.

  When dirt accumulates on the antifouling layer or the antifouling layer deteriorates to cause coloring, the absorption of visible light and infrared rays increases due to the fouling and / or coloring. May decrease. Therefore, it is preferable that the antifouling layer can maintain the initial gloss and hue. Specifically, the glossiness (JIS K7105.5.2) retention after 1000 hours of sunshine weatherometer weather resistance acceleration test (JIS K7350-4) is preferably 80 to 100%, particularly preferably 90 to 100%. The color difference ΔE (JIS K7105.5.4) after one year of outdoor exposure is preferably 0.1 to 5.0. Between the antifouling layer and the flexible resin coating layer, if necessary, an adhesive layer for improving the adhesion between the antifouling layer and the flexible resin coating layer, or preventing the resin from being decomposed by the photocatalyst. For example, an additive migration preventing layer for preventing the additive contained in the protective layer and the resin coating layer from migrating to the antifouling layer may be formed. In addition, a back surface adhesive layer for imparting high-frequency heat fusion property and hot air fusion property to the antifouling layer is formed on the surface opposite to the surface on which the antifouling layer is formed of the daylighting film material of the present invention. May be. Alternatively, while the daylighting film material is rolled up and stored, the additive contained in the adhesive layer on the back side or the flexible resin coating layer is transferred onto the antifouling layer and has antifouling properties. In order to prevent the lowering, an additive migration preventing layer may be formed on the back surface side (the surface opposite to the antifouling layer).

  The antifouling layer of the present invention preferably contains a photocatalytic substance. Examples of the photocatalytic substance used in the present invention include (1). Photocatalytic metal oxides such as titanium oxide (especially anatase type), tungsten oxide, iron oxide, zinc oxide, indium oxide, vanadium oxide, bismuth oxide, iron-tungsten oxide, (2). A cocatalyst-added (supported) photocatalyst obtained by adding (supporting) a metal such as silver, platinum, gold, copper, rhodium, palladium, ruthenium, and iridium as a promoter to the metal oxide of (1); (3). An anion-doped photocatalyst obtained by doping the photocatalytic metal oxide of (1) with nitrogen, carbon, sulfur, phosphorus, boron, fluorine, or the like; (4). (5) a cation-doped photocatalyst obtained by doping the photocatalytic metal oxide of (1) with a transition metal ion such as chromium, niobium, manganese, cobalt, vanadium, iron, or nickel; A co-doped photocatalyst obtained by doping the photocatalytic metal oxide of (1) with both an anion and a cation, (6). A metal halide-supported photocatalyst obtained by supporting a noble metal halide such as platinum, palladium or rhodium on the photocatalytic metal oxide of (1), (7). The oxygen deficient photocatalyst obtained by partially extracting oxygen from the photocatalytic metal oxide (1), etc. can be preferably used. A photocatalyst can be selected and used from the above, or one or a combination of two or more.

  Examples of the method for forming an antifouling layer containing a photocatalytic substance include a method of forming an antifouling layer containing a photocatalytic substance by applying a coating agent containing photocatalyst particles or sol and a binder, Conventionally known methods such as a method for forming an antifouling layer containing a photocatalytic substance from a solution of the substance by a sol-gel method, a method for forming an antifouling layer containing a photocatalytic substance by a sputtering method, an ion plating method, a CVD method, etc. It can form by the method of. As the binder, it is difficult to be decomposed by a photocatalyst and has a film forming ability, for example, an organic binder such as a fluorine resin, a silicone resin, an acrylic fluorine copolymer resin, an acrylic silicone copolymer resin, polysilazane, It is preferably a silicon compound condensation layer composed of any one or more of an organic silicate compound or a hydrolyzate (silanol group-containing silane compound) of a low condensate thereof, and further any one of silica sol, alumina sol, and titanium sol. The above may be included. The antifouling layer containing a photocatalytic substance preferably contains 10 to 70% by mass, particularly 20 to 60% by mass of particles or sol of the photocatalytic substance.

  The fibers used for the fiber base fabric used in the daylighting membrane material of the present invention include synthetic fibers such as polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, and vinylon fiber, natural fibers such as cotton and hemp, and half fibers such as acetate. Examples thereof include inorganic fibers such as synthetic fibers, glass fibers, silica fibers, alumina fibers, and carbon fibers. These fibers may be composed of single or a mixture of two or more kinds, and the shape thereof is a multifilament yarn, a short fiber. Any of fiber spun yarn, monofilament yarn, split yarn yarn, tape yarn yarn and the like may be used. 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, and patterned weave, but a plain weave fabric is preferably used because it has an excellent balance of the longitudinal properties of the obtained daylighting membrane material. 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 80% 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.

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

In the following examples, the light transmittance, the heat shielding rate, the gloss retention, and the test method for evaluating the color difference after one year of outdoor exposure are as follows.
(I) Light transmittance
It measured using Minolta spectrocolorimeter CM-3600d according to JIS Z8722.5.4 (condition g).
(II) Heat insulation rate
Test environment : Incandescent lamp (100V, 500W photoreflector lamp: daylight color) at the center of the ceiling of a box-shaped structure with an inside diameter of 45cm x width 35cm x length 35cm. Use: Toshiba Corp.) was attached, and a test environment for thermal insulation evaluation was configured. Next, a box-shaped frame with an outer diameter of 5 cm (height) x 10 cm (width) x 15 cm (length) is used as an adhesive with a square square cross section of 0.5 cm. An airtight test box was prepared by assembling and fixing the test membrane material to the four side surfaces, the upper surface portion, and the bottom surface portion of the box-type frame with a double-sided tape so that the surface thereof was outward. Further, a sensor of a heat flow meter (Shotrm HFM heat flow meter: manufactured by Showa Denko KK) was attached and fixed at the center of the bottom surface inside the test box. Attach a test box coated with a test membrane material (use a test membrane without a test membrane material for comparison) to the center of the bottom of the box-type structure, and connect the center point of the lamp to the center point of the test box The straight line direction was fixed so as to overlap the vertical direction. The distance from the lamp tip to the ceiling of the test box in the box structure was 35 cm. The box-shaped structure was installed in a constant temperature room at 20 ° C.
Test : Put a test box with no test membrane material in a box structure and keep it sealed, turn on the lamp, measure the heat flow (kcal / m ² h) every minute, heat after 30 minutes The flow rate qn (kcal / m ² h) was measured. After returning the temperature in the box structure to 20 ° C, the same as in the temperature-controlled room, put the test box with the test membrane material in the box structure, put it in a sealed state, turn on the lamp, and heat flow (kcal / m ² h) was measured every minute, the heat flow rate qc (kcal / m ² h) after 30 minutes was measured, and the heat shielding rate was determined by the following formula. The heat shielding rate was judged to be higher as the numerical value was higher.
Heat shielding rate (%) = [(qn−qc) / qn] × 100
(III) Gloss retention
According to the glossiness test method of JIS K7105.5.2, the initial glossiness G _Sb (60 °) on the surface side of the test membrane material and the glossiness G after 1000 hours of sunshine weatherometer accelerated weathering test (JIS K7350-4) _Sa (60 °) was measured, and the gloss retention was determined from the following formula.
Gloss retention (%) = [G _Sa (60 °) / G _Sb (60 °)] × 100
(IV) Color difference after one year of outdoor exposure An outdoor exposure test was conducted by setting the surface of the test membrane material facing upward on the outdoor exposure table at an inclination angle of 30 degrees southward, and the color of the initial test membrane material surface. The color difference ΔE (JIS K7105.5.4) from the surface color of the test membrane material 12 months after the exposure was measured.

In the following examples, the following base fabrics were used as the fiber base fabrics.
Base fabric 1: Polyester short fiber spun yarn non-coarse long plain woven fabric having the following structure and a mass of 230 g / m ²
295.3dtex (20th) /2×295.3dtex (20th) / 2
───────────────────────
55 x 48 (book / 25.4mm)
Base fabric 2: Polyester multifilament coarse long plain fabric with the following structure and mass of 210 g / m ²
833dtex (750d) / 3 × 833dtex (750d) / 3
───────────────────────
11 x 11 (book / 25.4mm)
Base fabric 3: Polyester multifilament coarse long plain fabric with the following structure and mass of 140 g / m ²
833dtex (750d) x 833dtex (750d)
───────────────────────
19 x 20 (book / 25.4mm)
Base fabric 4: Polyester multifilament coarse long plain fabric with a mass of 85 g / m ^{2 in} the following structure
1111dtex (1000d) × 1111dtex (1000d)
───────────────────────
10 x 10 (pieces / 25.4mm)

[Example 1]
Add the white colored vinyl ester resin stirred mixture of the following formulation 2 to the stirred mixture of the soft vinyl chloride resin paste of the following formulation 1 with respect to the mass of the vinyl chloride resin alone and stir to obtain the white colored vinyl ester resin. It was made to disperse | distribute uniformly and the incompatible resin mixture liquid 1 was obtained. In Formula 2, titanium oxide particles having an average particle diameter of 1000 nm were used as the heat-controllable colorant. The base fabric 1 is immersed in the liquid bath of the resin mixture liquid 1 and 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 then one side thereof. Was subjected to a mirror embossing treatment. Thus, the daylighting film in which the flexible resin coating layer having the sea-island structure was formed by adhering 300 g / m ^{2 of the} incompatible resin mixture liquid 1 in a state where the base fabric 1 was adhered to both surfaces and internally impregnated. The material was obtained. When the flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. For this daylighting film material, various evaluations were performed with the side subjected to the mirror embossing treatment as the front surface. The results are shown in Table 1.
<Formulation 1>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 parts by mass Zinc stearate (stabilizer) 2 parts by mass Stearic acid Barium (stabilizer) 2 parts by weight UV absorber: 0.5 parts by weight of benzotriazole

<Formulation 2>
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)
Thermally controllable colorant (titanium oxide: average particle size 1000 nm) 5 parts by mass

[Example 2]
On the flexible resin coating layer on the side subjected to the mirror embossing treatment of the film material obtained in the same manner as in Example 1, an antifouling layer coating solution of the following formulation 3 was coated with a gravure coater, and 120 ° C. For 3 minutes. Thus, a daylighting film material having an antifouling layer with a coating amount of 5 g / m ² formed on one surface was obtained. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 3>
100 parts by mass of fluoroolefin vinyl ether resin (Trademark: Fluorotop 1053: Asahi Glass Co., Ltd .: solid content 50% by mass)
Isophorone isocyanate curing agent 10 parts by mass (Trademark: Takenate D-140N: Takeda Pharmaceutical Co., Ltd .: solid content 75% by mass)
Silica (Trademark: Fine Seal X37: Tokuyama Corporation) 5 parts by weight Methyl ethyl ketone 100 parts by weight

[Example 3]
To the stirring mixture of the white colored soft vinyl chloride resin paste of the following formulation 4, 35% by mass of the vinyl ester resin stirring mixture of the following formulation 5 is added with respect to the mass of the vinyl chloride resin alone and stirred to uniformly disperse the vinyl ester resin. A flexible resin coating layer having a sea-island structure was formed in the same manner as in Example 1 by using the incompatible resin mixture liquid 3 thus prepared. In Formula 4, titanium oxide particles having an average particle diameter of 1000 nm were used as the heat-controllable colorant. The adhesion of the incompatible resin mixture liquid 3 to the base fabric 1 was 300 g / m ² . When this flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a colorless island component, and the soft vinyl chloride resin constituted a white sea component. The average particle size of the island components was 6.7 μm. Next, in the same manner as in Example 2, an antifouling layer having a coating amount of 5 g / m ² was formed on the flexible resin coating layer on the side subjected to the mirror embossing treatment to obtain a daylighting film material. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 4>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 parts by mass Zinc stearate (stabilizer) 2 parts by mass Stearic acid 2 parts by weight of barium (stabilizer) UV absorber: 0.5 parts by weight of benzotriazole series 2 parts by weight of heat-controllable colorant (titanium oxide: average particle size 1000 nm)

<Formulation 5>
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)

[Example 4]
The white colored silicone resin stirred mixture of the following formulation 7 is added to the stirred mixture of the soft vinyl chloride resin paste of the following formulation 6 with respect to the mass of the vinyl chloride resin alone and stirred to uniformly disperse the white colored silicone resin. An incompatible resin mixture solution 4 was obtained. As the heat-controllable colorant of Formulation 7, zinc oxide particles having an average particle diameter of 600 nm were used. The base fabric 1 is dipped in the liquid bath of this incompatible resin mixture liquid 4, 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. A sheet was obtained. As a result, in a state where the base fabric 1 was adhered to both surfaces and impregnated inside, the incompatible resin mixture liquid 4 was adhered at 270 g / m ² to form a flexible resin coating layer having a sea-island structure. Next, an incompatible resin mixture liquid 4 is coated on one surface of the PET film to a thickness of 0.05 mm, and this is overlaid on one side of the previously prepared sheet, and heated in an electric furnace at 180 ° C. for 5 minutes to produce a non-phase. After the molten resin mixture liquid 4 was solidified, the PET film was removed to form a 65 g / m ² smooth flexible resin coating layer. When these flexible resin coating layers were observed with a microscope, the silicone resin constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 3.4 μm. Next, a composition liquid of the following formulation 8 was applied to the flexible resin coating layer with a gravure coater, dried at 120 ° C. for 1 minute, and then cooled to form a 5 g / m ² resin intermediate layer on both surfaces. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 8 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, As a result, a total of 10 g / m ² of additive migration preventing layers composed of the resin intermediate layer and the additional resin layer were formed on both sides. Next, a coating solution for forming an adhesion / protection layer having the following composition 9 was applied on an additive migration prevention layer formed on the smooth flexible resin coating layer side with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled. Then, an adhesion / protection layer of 1.5 g / m ² is formed, and a coating solution for forming an antifouling layer having the following composition 10 is applied onto the adhesion / protection layer with a gravure coater, at 120 ° C. for 2 minutes. After drying, it was cooled to obtain a daylighting film material in which a 1.5 g / m ² photocatalytic substance-containing antifouling layer was formed on the smooth surface side. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 6>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 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 mass
Ultraviolet absorber: 0.5 parts by mass of benzotriazole series

<Formulation 7>
CY52-110 (silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd.)
Liquid A 50 parts by mass Liquid B 50 parts by mass Thermally controllable colorant (zinc oxide particles: average particle diameter 600 nm) 7 parts by mass

<Formulation 8>
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 9>
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 10>
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

[Example 5]
Add the white colored soft vinyl chloride resin paste of the following formulation 12 to the stirred mixture of the silicone resin stirred mixture of the following formulation 11 with respect to the mass of the silicone resin alone and stir to obtain the white colored soft vinyl chloride resin paste. A flexible resin coating layer having a sea-island structure was formed in the same manner as in Example 4 using the uniformly dispersed incompatible resin mixture liquid 5. Zinc oxide particles having an average particle size of 600 nm were used as the heat-controllable colorant of Formulation 12. The incompatible resin mixture liquid 5 adhered to both surfaces of the base fabric 1 and internally impregnated was 225 g / m ² , and the smooth flexible resin coating layer formed on one surface was 55 g / m ² . When these flexible resin coating layers were observed with a microscope, the vinyl chloride resin constituted a white island component and the silicone resin constituted a colorless sea component. The average particle size of the island components was 3.4 μm. Next, in the same manner as in Example 4, a total of 10 g / m ² of the additive migration preventing layer was formed on both sides, and 1.5 g was formed on the additive migration preventing layer formed on the smooth flexible resin coating layer side. / M ² adhesion / protection layer was formed, and a 1.5 g / m ² photocatalytic substance-containing antifouling layer was further formed on the adhesion / protection layer to obtain a daylighting film material. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 11>
CY52-110 (silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd.)
Liquid A 50 parts by mass Liquid B 50 parts by mass

<Formulation 12>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 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 mass
Ultraviolet absorber: 0.5 parts by mass of benzotriazole-based thermal control colorant (zinc oxide particles: average particle size 600 nm) 9 parts by mass

[Example 6]
To the stirring mixture of the soft vinyl chloride resin paste of Formulation 1, 35% by mass of the stirring mixture of yellow colored vinyl ester resin of Formula 13 shown below is added to the mass of the vinyl chloride resin alone and stirred to uniformly distribute the yellow colored vinyl ester resin. A flexible resin coating layer having a sea-island structure was formed in the same manner as in Example 1 using the dispersed incompatible resin mixture liquid 6. As the heat-controllable colorant of Formula 13, a Cr—Sb—Ti complex oxide (yellow) having an average particle diameter of 600 nm was used. The adhesion of the incompatible resin mixture liquid 6 to the base fabric 1 was 300 g / m ² . When this flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a yellow island component and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. Next, in the same manner as in Example 4, a total of 10 g / m ² of additive transfer prevention layer was formed on both sides, and 1.5 g / m ² on the additive transfer prevention layer formed on the side subjected to mirror embossing. An antifouling layer containing a photocatalytic substance of 1.5 g / m ² was further formed on the adhesive / protective layer to obtain a daylighting film material. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 13>
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)
Thermally controllable colorant (Cr—Sb—Ti composite oxide: average particle size 600 nm) 5 parts by mass

[Example 7]
To the stirring mixture of the soft vinyl chloride resin paste of Formulation 1, 35% by mass of the black colored vinyl ester resin of Formula 14 below was added to the mass of the vinyl chloride resin alone and stirred to uniformly disperse the black colored vinyl ester resin. Using the incompatible resin mixture liquid 7, a flexible resin coating layer having a sea-island structure was formed in the same manner as in Example 2. As the heat-controllable colorant of Formulation 14, a phthalocyanine-based dye (black: maximum absorption wavelength: 880 nm) was used. The incompatible resin mixture liquid 7 adhered to both surfaces of the base fabric 1 and internally impregnated was 300 g / m ² . When these flexible resin coating layers were observed with a microscope, the vinyl ester resin constituted a black island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. Next, in the same manner as in Example 4, a total of 10 g / m ² of the additive migration preventing layer was formed on both sides, and 1.5 g was formed on the additive migration preventing layer formed on the smooth flexible resin coating layer side. / M ² adhesion / protection layer was formed, and a 1.5 g / m ² photocatalytic substance-containing antifouling layer was further formed on the adhesion / protection layer to obtain a daylighting film material. Various evaluations were performed on this daylighting film material using the side on which the antifouling layer was formed as the surface. The results are shown in Table 1.
<Formulation 14>
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)
Thermally controllable colorant (Trademark: EEX Color HA-1: Nippon Shokubai Co., Ltd.) 0.1 parts by mass

[Comparative Example 1]
A film material was obtained in the same manner as in Example 2 except that a stirring mixture of the soft vinyl chloride resin paste of Formulation 1 was used instead of the incompatible resin mixture liquid 1. This film material was subjected to various evaluations using the side on which the antifouling layer was formed as the surface. The results are shown in Table 2.

[Comparative Example 2]
A film material was obtained in the same manner as in Example 3 except that a stirred mixture of white colored soft vinyl chloride resin paste of Formulation 4 was used instead of the incompatible resin mixture liquid 3. This film material was subjected to various evaluations using the side on which the antifouling layer was formed as the surface. The results are shown in Table 2.

[Comparative Example 3]
A membrane material was obtained in the same manner as in Example 2 except that titanium oxide was omitted from the white colored vinyl ester resin stirring mixture of Formulation 2. This film material was subjected to various evaluations using the side on which the antifouling layer was formed as the surface. The results are shown in Table 2.

  The daylighting film materials of Examples 1 to 7 have a sea-island structure in which the flexible resin coating layer is made of an incompatible mixture of a synthetic resin blend, and either the sea component or the island component is colored with heat controllability. The initial heat-shielding rate and light transmittance were high. In Examples 2 to 7, at least one antifouling layer was provided on the flexible resin coating layer, and the antifouling layer was subjected to a sunshine weatherometer accelerated weathering test (JIS K7350-4) after 1000 hours. Gloss retention rate is 80% or more, antifouling layer color difference after 1 year of outdoor exposure satisfies 5 or less, and heat insulation rate and light transmittance after 1 year of outdoor exposure were maintained with almost no decrease. . In particular, in Examples 4 to 7 in which the antifouling layer contains a photocatalytic substance, there is almost no change in hue and gloss even after one year of outdoor exposure, and there is almost no change in the heat shielding rate and light transmittance. It was. Examples 2 and 3 are an example in which the island component is colored and an example in which the sea component is colored, respectively. In either case, the heat shielding rate is high. Regarding the light transmittance, Example 3 shows a lower value, but this is because a sea component having a large volume ratio in the flexible resin coating layer was colored, and thus a large amount of visible light was scattered. Conceivable. However, in comparison with Example 3 and Comparative Example 2 (the flexible resin coating layer does not have a sea-island structure and the entire flexible resin coating layer is colored), the heat shielding rate of Example 3 is significantly higher. In addition, the light transmittance was slightly superior. Example 4 and Example 5 are examples in which the island component is colored, but the resin serving as the base of the sea component and the island component is opposite, and in Example 4, the sea component is higher than the refractive index of the island component. In Example 5, the island component has a higher refractive index than the sea component. Although these were the same in terms of light transmittance, the results of Example 5 in which the refractive index of the island component was higher than the refractive index of the sea component were slightly superior with respect to the heat shielding rate. From this result, it can be seen that the higher the refractive index of the island component than the refractive index of the sea component, the higher the heat shielding effect by the refractive scattering phenomenon at the interface between the sea component and the island component. Example 6 is an example in which the island component is colored with an infrared-reflective metal composite oxide, and the heat shielding property is slightly inferior to Example 2 in which the island component is white-colored with a metal oxide, but is colored in a chromatic color. The obtained daylighting film material was obtained, and the heat shielding rate was higher than that of Comparative Example 3 in which the island component did not contain the heat-controllable colorant. Example 7 is an example in which the island component is colored by including an infrared absorbing substance, and both the heat shielding rate and the light transmittance are slightly inferior to Example 2 in which the island component is white-colored with a metal oxide. The heat shielding rate was higher than that of Comparative Example 3 in which the component did not contain a heat-controllable colorant. The film material of Comparative Example 1 has a heat shielding property although the flexible resin coating layer does not have a sea-island structure and does not contain a heat-controllable colorant, but has a higher light transmittance than that of Example 2. There was no film material. Although the film material of Comparative Example 2 has a higher heat shielding rate than the film material of Comparative Example 1 due to the heat-controllable colorant contained in the entire flexible resin coating layer, the flexible resin layer has a sea-island structure. Therefore, the light transmittance was significantly low. Since the film material of Comparative Example 3 does not contain a heat-controllable colorant, the light transmittance is as high as that of Comparative Example 1 and has a sea-island structure, so refraction at the interface between the sea component and the island component. Although the heat shielding rate was higher than that of Comparative Example 1 due to the scattering phenomenon, both the sea component and the island component did not contain a heat-controllable colorant, and thus the heat shielding effect was insufficient.

[Example 8]
Add 80% by mass of the white colored vinyl ester resin stirred mixture of Formula 2 to the stirred mixture of the soft vinyl chloride resin paste of Formula 1 with respect to the mass of the vinyl chloride resin alone, and uniformly disperse the white colored vinyl ester resin. An incompatible resin mixture liquid 8 was obtained. The base fabric 2 was dipped in the liquid bath of this incompatible resin mixture liquid 8, 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. . As a result, the incompatible resin mixture liquid 8 was impregnated with 250 g / m ² to obtain a mesh-like film material on which a flexible resin coating layer having a sea-island structure was formed. When this flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a white island component, and the soft PVC resin constituted a colorless sea component. The average particle size of the island components was 6.4 μm. Subsequently, the mesh-like film material is immersed in an adhesion / protection layer treatment solution of Formulation 9, then pressed with mangle roll, dried at 100 ° C. for 1 minute, and then cooled to obtain a 1.0 g / m ² adhesion protection layer. Formed. Further, after immersing the mesh-like film material with an adhesion protective layer in the coating solution for forming the antifouling layer of Formulation 10, squeezed with mangle roll, dried at 100 ° C. for 1 minute, cooled, and 1.5 g / m ² photocatalyst. An antifouling layer containing an active substance was formed to form a mesh-shaped daylighting film material. Since there was no structural difference between the front and back surfaces of the mesh-shaped daylighting film material, various evaluations were performed with a mark on one surface after the film material was formed and the side with the mark as the surface. The results are shown in Table 3.

[Comparative Example 4]
A mesh-like film material was obtained in the same manner as in Example 8 except that a stirred mixture of white colored soft vinyl chloride resin paste of Formulation 4 was used instead of the incompatible resin mixture liquid 8. Since there was no structural difference between the front and back surfaces of the mesh-like film material, various evaluations were performed using a mark on one surface after the film material was formed and the side with the mark as the surface. The results are shown in Table 3.

  Example 8 is a mesh-shaped daylighting film material obtained by impregnating and covering a coarse base fabric with a sea-island flexible resin. Since infrared rays are transmitted through the mesh eyes, the heat shielding rate is low as compared with Examples 1 to 7, but the light transmittance is much higher, and the daylighting film can be seen through the other side of the membrane material through the mesh eyes. It was a material. Further, in comparison with Comparative Example 4 (the flexible resin coating layer does not have a sea-island structure and is colored white), as shown in Table 3, Example 8 is excellent in both light transmittance and heat shielding rate. It was.

[Example 9]
To the hot melt kneaded product of the soft fluorine resin of the following formulation 15 is added 10% by mass of the hot-melt kneaded product of the white colored vinyl chloride resin of the following blend 16 with respect to the mass of the soft fluororesin alone, and then hot melt kneaded with a Banbury mixer. Then, an incompatible resin mixture 9 was obtained by uniformly dispersing the white colored vinyl chloride resin. The resin mixture 9 was passed through four calendar rolls set at 180 ° C. to form a film 9-1 having a thickness of 0.25 mm. On the other hand, a hot melt kneaded product of soft fluororesin with the following formulation 15 was passed through four calender rolls set at 180 ° C. to form a transparent film 9-2 having a thickness of 0.25 mm. Next, the base fabric 3 was inserted between the obtained film 9-1 and film 9-2 and laminated by thermocompression bonding to obtain a daylighting film material. When the flexible resin coating layer made of the film 9-1 was observed with a microscope, the vinyl chloride resin constituted a white island component, and the soft fluororesin constituted a colorless sea component. The average particle size of the island components was 2.8 μm. For this daylighting film material, various evaluations were performed using the side on which the film 9-1 was laminated as the surface. The results are shown in Table 4.
<Formulation 15>
100 parts by mass of soft fluororesin (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin)

<Formulation 16>
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 mass
Ultraviolet absorber: 0.5 parts by mass of benzotriazole-based thermal control colorant (titanium oxide particles: average particle size 1000 nm) 5 parts by mass

[Example 10]
Add 20% by mass of the hot-melt kneaded mixture of the white colored styrene butadiene block copolymer of the following formulation 18 to the hot-melt kneaded product of the soft vinyl chloride resin of the following formulation 17 with the Banbury mixer. By melt-kneading, an incompatible resin mixture 10 in which a white colored styrene butadiene block copolymer was uniformly dispersed was obtained. Titanium oxide particles having an average particle diameter of 1000 nm were used as the heat controllable colorant. This incompatible resin mixture 10 was passed through four calendar rolls set at 180 ° C. to form a film 10-1 having a thickness of 0.25 mm. On the other hand, a hot melt kneaded product of soft vinyl chloride resin having the following composition 17 was passed through four calender rolls set at 180 ° C. to form a transparent film 10-2 having a thickness of 0.25 mm. Next, the base fabric 3 was inserted between the obtained films 10-1 and 10-2, and laminated by thermocompression to obtain a sheet. When the flexible resin coating layer made of the film 10-1 was observed with a microscope, the styrene-butadiene block copolymer constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 10.5 μm. Next, an additive migration prevention layer is formed on both sides of the sheet in the same manner as in Example 3, an adhesion / protection layer is formed on the additive migration prevention layer on the film 10-1 side, and further on the adhesion / protection layer. A 1.5 g / m ² antifouling layer was formed to obtain a daylighting film material. For this daylighting film material, various evaluations were performed using the side on which the film 10-1 was laminated as the surface. The results are shown in Table 4.
<Formulation 17>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 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

<Formulation 18>
100 parts by mass of styrene / butadiene block copolymer (product name: Asaflex 830, manufactured by Asahi Kasei Chemicals Corporation)
Thermally controllable colorant (titanium oxide particles: average particle size 1000 nm) 5 parts by mass

[Example 11]
Add 20% by mass of the hot-melt kneaded mixture of the white-colored styrene butadiene block copolymer of Formulation 18 to the hot-melt kneaded product of the yellow-colored soft vinyl chloride resin of Formulation 19 shown below with respect to the mass of the vinyl chloride resin alone, using a Banbury mixer. The incompatible resin mixture 11 in which the white colored styrene butadiene block copolymer was uniformly dispersed was obtained by hot melt kneading. As a heat-controllable colorant of Formulation 19, a complex oxide (yellow) of Cr—Sb—Ti having an average particle diameter of 50 nm was used. This incompatible resin mixture 11 was passed through four calendar rolls set at 180 ° C. to form a film 11-1 having a thickness of 0.25 mm. On the other hand, a hot melt kneaded product of the soft vinyl chloride resin of Formulation 17 was passed through four calender rolls set at 180 ° C. to form a transparent film 11-2 having a thickness of 0.25 mm. Next, the base fabric 3 was inserted between the obtained film 11-1 and film 11-2 and laminated by thermocompression bonding to obtain a sheet. When the flexible resin layer made of the film 11-1 was observed with a microscope, the styrene-butadiene block copolymer constituted a white island component, and the soft vinyl chloride resin constituted a yellow sea component. The average particle size of the island components was 10.5 μm. Next, an additive migration prevention layer is formed on both sides of the sheet in the same manner as in Example 3, an adhesion / protection layer is formed on the additive migration prevention layer on the film 11-1 side, and further on the adhesion / protection layer. A 1.5 g / m ² photocatalytic substance-containing antifouling layer was formed to obtain a daylighting film material. For this daylighting film material, various evaluations were performed using the side on which the film 11-1 was laminated as the surface. The results are shown in Table 4.
<Formulation 19>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 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-based 0.5 part by weight Thermally controllable colorant (Cr-Sb-Ti composite oxide: average particle size 50 nm) 2 Parts by mass

[Example 12]
In the same manner as in Example 11, a daylighting film material was obtained. However, the heat-controllable colorant in Formulation 19 is 2 parts by mass of Co-Al composite oxide (blue) having an average particle diameter of 50 nm, and the white-colored styrene of Formulation 18 is added to a hot-melt kneaded product of blue-colored soft vinyl chloride resin. A film 12-1 having a thickness of 0.25 mm was formed from an incompatible resin mixture 12 in which a hot melt kneaded product of a butadiene block copolymer was added and uniformly dispersed by adding 20% by mass with respect to the mass of the vinyl chloride resin alone. It used instead of the film 11-1. When the flexible resin layer made of the film 12-1 was observed with a microscope, the styrene-butadiene block copolymer constituted a white island component, and the soft vinyl chloride resin constituted a blue sea component. The average particle size of the island components was 10.5 μm. Various evaluations were performed using the side of the daylighting film material on which the film 12-1 was laminated as the surface. The results are shown in Table 4.

[Comparative Example 5]
Instead of the film 11-1 molded from the incompatible resin mixture 11, a yellow colored soft vinyl chloride resin film having a thickness of 0.25 mm molded from a hot-melt kneaded product of the yellow colored soft vinyl chloride resin of Formulation 19 is used. A membrane material was obtained in the same manner as in Example 8 except that. Various evaluations were performed using the surface of the film material on which the yellow colored soft vinyl chloride resin film was laminated as the surface. The results are shown in Table 4.

  Examples 9 and 10 are daylighting membrane materials in which a calendar film is laminated on both sides of a base fabric as a flexible resin coating layer. A flexible resin layer containing a metal oxide as an island component is laminated on one side, and a transparent film is laminated on the other side, both having high light transmission equivalent to those of Examples 1 to 5. Rate and heat insulation rate. When Example 9 and Example 10 were compared, Example 9 was larger in the island component volume ratio, so that the heat shielding rate was higher than Example 10 and the translucency was low. In Examples 11 and 12, the sea component of the flexible resin coating layer in Example 10 is further added with a chromatic color heat-controllable colorant composed of a metal composite oxide, and a certain degree of light transmittance is maintained. However, a chromatic color heat insulating daylighting film material exhibiting high heat insulating properties was obtained. The reason why the light transmittance of Examples 11 and 12 is lower than that of Example 10 is that a part of visible light is absorbed or reflected by the chromatic color heat-controllable colorant. However, by using a heat-controllable metal composite oxide, the heat shielding rate was equivalent or rather high. Further, according to a comparison between Example 11 and Comparative Example 5 (the entire flexible resin coating layer is colored yellow with a heat-controllable colorant and does not have a sea-island structure), Example 11 is acceptable. The flexible resin layer had a sea-island structure, and the heat shielding rate was significantly high because the island component contained a metal oxide.

[Example 13]
60 wt% of the white colored vinyl ester resin stirred mixture of Formulation 2 is added to the stirred mixture of the soft vinyl chloride resin paste of Formulation 1 with respect to the mass of the vinyl chloride resin alone, and the white colored vinyl ester resin is uniformly dispersed. An incompatible resin mixture liquid 13 was obtained. The base fabric 4 is immersed in the liquid bath of the obtained incompatible resin mixture liquid 13 and 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. went. As a result, the incompatible resin mixture liquid 13 was impregnated with 70 g / m ² to obtain a mesh-like fiber base fabric on which a flexible resin coating layer was formed. When the flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. Subsequently, the hot-melt kneaded product of the soft vinyl chloride resin of Formulation 18 was passed through four calender rolls set at 180 ° C. to form a transparent film having a thickness of 0.25 mm, and the mesh-like fiber base fabric obtained previously A sheet with transparency was obtained by laminating both surfaces of the sheet by thermocompression bonding. Next, the composition solution of Formulation 8 was applied on the laminated calendar film with a gravure coater, dried at 120 ° C. for 1 minute, and then cooled to form a 5 g / m ² resin intermediate layer on both sides. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 8 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, As a result, a total of 10 g / m ² of additive migration preventing layers composed of the resin intermediate layer and the additional resin layer were formed on both sides. Next, the adhesive / protective layer-forming coating solution of Formulation 9 was applied onto the additive migration-preventing layer with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled to a 1.5 g / m ² adhesive / protective layer. Is coated on the adhesive / protective layer with a gravure coater, dried at 120 ° C. for 2 minutes, and then cooled to a 1.5 g / m ² photocatalyst. A daylighting film material in which an antifouling layer containing an active substance was formed on both surfaces was obtained. Since there was no structural difference between the front and back surfaces of this daylighting film material, various evaluations were performed with a mark on one surface after the daylighting film material was formed and the side with the mark as the surface. The results are shown in Table 5.

[Example 14]
Substrate 4 is dipped in a liquid bath of a stirred mixture of the soft vinyl chloride resin paste of Formulation 1. The fabric is 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. Went. As a result, a stirring mixture of soft vinyl chloride resin paste was impregnated with 70 g / m ² to obtain a mesh-like fiber base fabric on which a flexible resin coating layer was formed. On the other hand, the immiscible resin mixture 10 obtained in the same manner as in Example 10 was passed through four calender rolls set at 180 ° C. to form a 0.25 mm-thick film 14-1, and the composition 18 soft A polyvinyl chloride resin hot melt kneaded product was passed through four calendar rolls set at 180 ° C. to form a transparent film 14-2 having a thickness of 0.25 mm. Next, the obtained mesh-like fiber base fabric was inserted between the obtained films 14-1 and 14-2, and laminated by thermocompression to obtain a sheet. When the flexible resin layer made of the film 14-1 was observed with a microscope, the styrene-butadiene block copolymer constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 10.5 μm. Next, the composition liquid of Formulation 8 was coated on a calender film laminated in the same manner as in Example 13 with a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form a 5 g / m ² resin intermediate layer on both surfaces. did. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 8 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, As a result, a total of 10 g / m ² of additive migration preventing layers composed of the resin intermediate layer and the additional resin layer were formed on both sides. Next, the adhesive / protective layer-forming coating solution of Formulation 9 was applied onto the additive migration-preventing layer with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled to a 1.5 g / m ² adhesive / protective layer. Further, a coating solution for forming an antifouling layer of Formulation 10 was applied onto the adhesive / protective layer with a gravure coater, dried at 120 ° C. for 2 minutes, and then cooled to 1.5 g / m ² of antifouling layer. A daylighting film material having a dirty layer formed on both sides was obtained. For this daylighting film material, various evaluations were performed using the side on which the film 14-1 was laminated as the surface. The evaluation results are shown in Table 5.

[Example 15]
After immersing the base fabric 4 in the liquid bath of the incompatible resin mixture liquid 1 obtained in the same manner as in Example 1 and pulling it up, the base cloth 4 is pressed with a mangle roll and gelled at 150 ° C. for 1 minute. Heat treatment was carried out at a temperature of 1 minute. As a result, an incompatible resin mixture liquid 1 was impregnated with 70 g / m ² to obtain a mesh-like fiber base fabric on which a flexible resin coating layer was formed. When the flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. On the other hand, 17% by mass of the hot-melt kneaded mixture of the white-colored styrene butadiene block copolymer of Formulation 19 is added to the hot-melt kneaded product of the soft vinyl chloride resin of Formulation 18 with respect to the mass of the vinyl chloride resin alone, and heated with a Banbury mixer. By melt-kneading, an incompatible resin mixture 15 in which a white colored styrene butadiene block copolymer was uniformly dispersed was obtained. This incompatible resin mixture 15 was passed through four calendar rolls set at 180 ° C. to form a film 15-1 having a thickness of 0.25 mm. In addition, a hot melt kneaded product of the soft vinyl chloride resin of Formulation 18 was passed through four calendar rolls set at 180 ° C. to form a transparent film 15-2 having a thickness of 0.25 mm. Subsequently, the mesh-like fiber base fabric obtained previously was inserted between the obtained films 15-1 and 15-2, and laminated by thermocompression to obtain a sheet. When the flexible resin coating layer made of the film 15-1 was observed with a microscope, the styrene-butadiene block copolymer constituted a white island component, and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 10.5 μm. Next, the composition solution of Formulation 8 was applied on the laminated calendar film with a gravure coater, dried at 120 ° C. for 1 minute, and then cooled to form a 5 g / m ² resin intermediate layer on both sides. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 8 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, As a result, a total of 10 g / m ² of additive migration preventing layers composed of the resin intermediate layer and the additional resin layer were formed on both sides. Next, the adhesive / protective layer-forming coating solution of Formulation 9 was applied onto the additive migration-preventing layer with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled to a 1.5 g / m ² adhesive / protective layer. Is coated on the adhesive / protective layer with a gravure coater, dried at 120 ° C. for 2 minutes, and then cooled to a 1.5 g / m ² photocatalyst. A daylighting film material in which an antifouling layer containing an active substance was formed on both surfaces was obtained. For this daylighting film material, various evaluations were performed using the side on which the film 15-1 was laminated as the surface. The evaluation results are shown in Table 5.

[Example 16]
60% by mass of the black colored vinyl ester resin stirred mixture of Formulation 14 is added to the stirred mixture of the soft vinyl chloride resin paste of Formulation 1 with respect to the mass of the vinyl chloride resin alone, and the black colored vinyl ester resin is uniformly dispersed. Incompatible resin mixture liquid 16 was obtained. The base fabric 4 is immersed in the liquid bath of the obtained incompatible resin mixture liquid 16 and 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. went. As a result, an incompatible resin mixture solution 16 was impregnated with 70 g / m ² to obtain a mesh-like fiber base fabric on which a flexible resin coating layer was formed. When this flexible resin coating layer was observed with a microscope, the vinyl ester resin constituted a black island component and the soft vinyl chloride resin constituted a colorless sea component. The average particle size of the island components was 6.7 μm. Subsequently, the hot-melt kneaded product of the soft vinyl chloride resin of Formulation 18 was passed through four calender rolls set at 180 ° C. to form a transparent film having a thickness of 0.25 mm, and the mesh-like fiber base fabric obtained previously A sheet with transparency was obtained by laminating both surfaces of the sheet by thermocompression bonding. Next, the composition solution of Formulation 8 was applied on the laminated calendar film with a gravure coater, dried at 120 ° C. for 1 minute, and then cooled to form a 5 g / m ² resin intermediate layer on both sides. Furthermore, on the resin intermediate layer, a solvent diluted solution obtained by removing silica from the resin composition of Formulation 8 was applied using a gravure coater, dried at 120 ° C. for 1 minute and then cooled to form an additional resin layer, As a result, a total of 10 g / m ² of additive migration preventing layers composed of the resin intermediate layer and the additional resin layer were formed on both sides. Next, the adhesive / protective layer-forming coating solution of Formulation 9 was applied onto the additive migration-preventing layer with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled to a 1.5 g / m ² adhesive / protective layer. Is coated on the adhesive / protective layer with a gravure coater, dried at 120 ° C. for 2 minutes, and then cooled to a 1.5 g / m ² photocatalyst. A daylighting film material in which an antifouling layer containing an active substance was formed on both surfaces was obtained. Since there was no structural difference between the front and back surfaces of this daylighting film material, various evaluations were performed with a mark on one surface after the daylighting film material was formed and the side with the mark as the surface. The results are shown in Table 5.

[Comparative Example 6]
Substrate 4 is dipped in a liquid bath of a stirred mixture of the soft vinyl chloride resin paste of Formulation 1. The fabric is 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. Went. As a result, a mesh-like fiber base fabric in which the soft vinyl chloride resin of Formulation 1 was impregnated with 70 g / m ² was formed. Subsequently, the hot melt kneaded product of the soft vinyl chloride resin of Formulation 18 was passed through four calendar rolls set at 180 ° C. to form a transparent film having a thickness of 0.25 mm, and the mesh-like fiber base fabric formed earlier A sheet with transparency was obtained by laminating on both sides. Subsequently, in the same manner as in Example 13, an additive migration preventing layer, an adhesion / protective layer, and a photocatalytic substance-containing antifouling layer were formed on both surfaces of the sheet to obtain a film material. Since there was no structural difference between the front and back surfaces of this film material, various evaluations were performed with a mark on one surface after the film material was formed and the side with the mark as the surface. The results are shown in Table 6.

[Comparative Example 7]
Substrate 4 is dipped in a liquid bath of a stirred mixture of the soft vinyl chloride resin paste of Formulation 1. The fabric is 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. Went. As a result, a mesh-like fiber base fabric in which the soft vinyl chloride resin of Formulation 1 was impregnated with 70 g / m ² was formed. Subsequently, the hot melt kneaded product of the soft vinyl chloride resin having the following composition 21 was passed through four calendar rolls set at 180 ° C. to form a film having a thickness of 0.25 mm to form a ratio 7-1. Moreover, the hot-melt kneaded material of the soft vinyl chloride resin of the blend 18 was passed through four calendar rolls set at 180 ° C. to form a transparent film ratio 7-2 having a thickness of 0.25 mm. Next, the obtained mesh-like fiber base fabric was inserted between the obtained film (ratio) 7-1 and film (ratio) 7-2, and laminated by thermocompression to obtain a sheet. Subsequently, in the same manner as in Example 13, an additive migration preventing layer, an adhesion / protective layer, and a photocatalytic substance-containing antifouling layer were formed on both surfaces of the sheet to obtain a film material. About this film | membrane material, the side which laminated | stacked film (ratio) 7-1 was evaluated as the surface. The results are shown in Table 6.
<Formulation 21>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 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-based 0.5 part by weight Thermally controllable colorant (titanium oxide particles: average particle size 1000 nm) 2 parts by weight

[Comparative Example 8]
The base fabric 4 is immersed in a liquid bath of a stirring mixture of the white colored soft vinyl chloride resin paste of Formulation 4, which is pulled up and simultaneously pressed with a mangle roll, gelled at 150 ° C. for 1 minute, then 1 at 190 ° C. By performing the heat treatment for 5 minutes, a mesh-like fiber base fabric having 70 g / m ^{2 of} impregnated white colored soft vinyl chloride resin of Formulation 4 adhered thereto was formed. Subsequently, the hot melt kneaded product of the soft vinyl chloride resin of Formulation 18 was passed through four calendar rolls set at 180 ° C. to form a transparent film having a thickness of 0.25 mm, and the mesh-like fiber base fabric formed earlier A sheet with transparency was obtained by laminating both surfaces of the sheet by thermocompression bonding. Subsequently, in the same manner as in Example 13, an additive migration preventing layer, an adhesion / protective layer, and a photocatalytic substance-containing antifouling layer were formed on both surfaces of the sheet to obtain a film material. Since there was no structural difference between the front and back surfaces of this film material, various evaluations were performed with a mark on one surface after the film material was formed and the side with the mark as the surface. The results are shown in Table 6.

[Comparative Example 9]
A film material was obtained in the same manner as in Example 16 except that instead of the incompatible resin mixture liquid 16, a stirred mixture of black colored soft vinyl chloride resin paste having the following formulation 21 was used. Since there was no structural difference between the front and back surfaces of this film material, various evaluations were performed with a mark on one surface after the film material was formed and the side with the mark as the surface. The results are shown in Table 6.
<Formulation 22>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1600) 100 parts by mass Tricresyl phosphate (plasticizer) 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 120 parts by mass Zinc stearate (stabilizer) 2 parts by mass Stearic acid Barium (stabilizer) 2 parts by weight UV absorber: benzotriazole 0.5 part by weight Colorant (carbon black) 2 parts by weight

  In Example 13, the flexible resin coating layer impregnated and adhered to the base fabric has a sea-island structure (island components are colored white by metal oxide particles), and the mesh-like fiber base fabric impregnated and adhered to the flexible resin is used. A transparent calender film is laminated on both sides and is a daylighting film material having transparency. Since infrared rays are transmitted through the mesh-shaped fiber base fabric, the heat shielding rate is somewhat lower than in the other examples, but the light transmittance is very high. Further, in comparison with Comparative Example 6 (both the impregnated flexible resin coating layer and the calender film do not have a sea-island structure and are not colored), the heat shielding rate is greatly exceeded. It was confirmed that the sea-island-shaped flexible resin coating layer impregnated and adhered to the base fabric of Example 13 greatly contributed to the improvement of the heat shielding property. Furthermore, in comparison with Comparative Example 9 (a white colored colored flexible resin not having a sea-island structure is impregnated and adhered to the base fabric and transparent calendar films are laminated on both sides), both are transparent film materials. Although there is no difference in appearance, both the light transmittance and the heat shielding rate exceed, the flexible resin coating layer impregnated and adhered to the base fabric has a sea-island structure, and the island component contains metal oxide particles. It was confirmed that the light transmittance was improved and the heat shielding property was improved by being colored white. In Example 14, a calender film having a sea-island structure was laminated on one side of a base fabric impregnated and coated with a transparent flexible resin, and a transparent calender film was laminated on the other side. One calendar film is not transparent, has a sea-island structure, and the island component is white-colored. Therefore, the light transmittance is lower than that in Example 13, but infrared rays are transmitted through the mesh-like fiber base fabric. The heat shielding rate has been improved in order to prevent this. Furthermore, in comparison with Comparative Example 7 (a white-colored calender film having a non-colored flexible resin impregnated and adhered to the base fabric and having no sea-island structure on one side), both the light transmittance and the heat shielding rate are compared. It was higher. In Example 15, both the flexible resin coating layer impregnated and adhered to the base fabric and the calendar film have a sea-island structure, and the island components are colored white. By making it lower than Examples 13 and 14, the heat shielding rate could be improved without reducing the light transmittance. In Example 16, the flexible resin coating layer impregnated and adhered to the base fabric has a sea-island structure, and the island component is black-colored with an infrared absorbing material. A transparent calender film is laminated on both sides and is a daylighting film material having transparency. Although the heat shielding properties were slightly inferior to those of Example 13, the light transmittance was the same. Moreover, since the mesh-like fiber base fabric is colored black and the irregular reflection of visible light at the fiber base fabric portion is suppressed, the daylighting membrane material that has better transparency than Example 13 and can clearly see the other side of the membrane material clearly. Met. On the other hand, Comparative Example 9 is an effect of carbon black contained in the soft PVC resin impregnated and adhered to the mesh-like fiber base fabric, so that irregular reflection of visible light at the fiber base fabric portion is suppressed, and excellent transparency as in Example 16 is achieved. However, since the flexible resin layer does not have a sea-island structure, the film material is inferior in heat shielding properties.

  The heat-insulating surname light-collecting film material obtained by the present invention is light-transmissive, transparent, colored transparent, colored translucent, colored opaque, etc. In addition, it is possible to provide an environment that has been difficult to achieve in the past, such as being cool, and it is also possible to select colorful colors in terms of design. Therefore, especially when used for awning tents, awning monuments, decorative tents, tent warehouses, event tents, truck hoods, blinds, partitions, seat shutters, agricultural and horticultural seats, etc. It is possible to reduce energy consumed for lighting and cooling.

1: Heat shielding daylighting film material 2: Fiber base fabric 3: Flexible resin coating layer (sea-island structure)
4: Sea component 4-1: Sea component containing a heat-controllable colorant 4-2: Sea component not containing a heat-controllable colorant 5: Island component 5-1: Island component containing a heat-controllable colorant 5- 2: Island component not containing heat-controllable colorant 6: Antifouling layer

Claims (15)

  A flexible membrane material comprising a fiber base fabric and a flexible resin coating layer formed on at least one surface thereof and having a light transmittance (measured according to JIS Z8722.5.4 (condition g)) of 3 to 70%. And at least one of the flexible resin coating layers has a sea-island structure composed of an incompatible mixture of synthetic resin blends, and in the sea-island structure, either the sea component or the island component is thermally controllable. A heat shielding daylighting film material comprising a colorant.   In the sea-island structure, there is a difference between the refractive index of the synthetic resin constituting the sea component and the refractive index of the synthetic resin constituting the island component, the refractive index difference is 0.05 or more, and in the sea component The heat shielding daylighting film material according to claim 1, wherein an average particle diameter of the island component dispersed in the water is 0.5 to 20.0 μm.   The heat-shielding light-collecting film material according to claim 1, wherein the heat-controllable colorant includes one or more selected from metal oxide fine particles, metal composite oxide fine particles, and a near-infrared absorbing material.   The metal oxide fine particles are titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, chromium oxide, iron oxide, tin-doped indium oxide, indium-doped tin oxide, and antimony-doped tin oxide. The heat-shielding daylighting film material according to claim 3, comprising at least one selected.   From the metal composite oxide, wherein the metal composite oxide fine particles comprise two or more components of titanium, zinc, antimony, iron, nickel, cobalt, chromium, magnesium, copper, manganese, aluminum, niobium, and silicon. The heat-shielding daylighting film material according to claim 3, comprising at least one selected.   The said near-infrared absorptive substance contains 1 or more types chosen from the phthalocyanine type compound, the naphthol quinone type compound, the immonium type compound, the anthraquinone type compound, the aminium type compound, and the nickel-thiol type complex compound. The heat shielding daylighting film material described.   An antifouling layer is provided on the flexible resin coating layer, and the glossiness (JIS K7105.5.2) retention after 1000 hours according to the sunshine weatherometer accelerated weathering test (JIS K7350-4) is 80-100. The heat-shielding daylighting film material according to claim 1, which is%.   An antifouling layer is provided on the flexible resin coating layer, and a color difference ΔE (JIS K7105.5.4) between before outdoor exposure and after one year is 0.1 to 5.0. The heat-shielding daylighting film material according to any one of the above.   The heat-shielding daylighting film material according to claim 7 or 8, wherein the antifouling layer contains a photocatalytic substance.   A heat-shielding daylighting film material comprising: a fiber base fabric; and a flexible resin coating layer having a sea-island structure in which either a sea component or an island component contains a heat-controllable coloring agent. Constructed by a compatible pair, one of the synthetic resin immiscible pair as a heat-controllable colorant-containing synthetic resin, and the other of the heat-controllable colorant-containing synthetic resin and the synthetic resin non-compatible pair The synthetic resin is mixed, and the average particle size of the island component dispersed in the sea component is set to 0.5 to 20.0 μm.   The said sea island structure has a difference in the refractive index of the synthetic resin which comprises a sea component, and the refractive index of the synthetic resin which comprises an island component, The refractive index difference is 0.05 or more. Manufacturing method of heat-shielding daylighting film material.   The method for producing a heat-shielding daylighting film material according to claim 10, wherein the heat-controllable colorant contains one or more selected from metal oxide fine particles, metal composite oxide fine particles, and a near-infrared absorbing material.   The metal oxide fine particles are titanium oxide, zinc oxide, tin oxide, zirconium oxide, indium oxide, antimony trioxide, tungsten oxide, chromium oxide, iron oxide, tin-doped indium oxide, indium-doped tin oxide, and antimony-doped tin oxide. The manufacturing method of the heat-shielding daylighting film material according to claim 12, comprising at least one selected.   From the metal composite oxide, wherein the metal composite oxide fine particles comprise two or more components of titanium, zinc, antimony, iron, nickel, cobalt, chromium, magnesium, copper, manganese, aluminum, niobium, and silicon. The manufacturing method of the heat-shielding daylighting film material according to claim 12, comprising at least one selected. The near-infrared absorbing substance includes at least one selected from a phthalocyanine compound, a naphtholquinone compound, an imonium compound, an anthraquinone compound, an aminium compound, and a nickel-thiol complex compound. The manufacturing method of the heat-shielding daylighting film material of description.