JP2018001697A - Flexible lighting control sheet - Google Patents

Abstract

The light transmittance of a sheet is controlled in gradation, and particularly when the surface temperature of the sheet reaches a high temperature during the daytime, the light transmittance of the sheet body is attenuated in gradation to produce a light-shielding curtain effect. The light temperature of the light control sheet can be repeated several times, and the light transmittance increases in gradation in the evening, so that the indoor lighting can be secured repeatedly, and the light control sheet has excellent weather resistance. Provided. A light-transmitting laminate comprising a surface protective layer and a back surface resin layer, and a temperature-sensitive color-changing resin layer in between, wherein at least the surface protective layer is semi-transparent and has ultraviolet shielding properties. 1) a resin layer containing white fine particles and an ultraviolet absorber, or 2) a layer containing an ultraviolet absorber in an incompatible resin blend, and the temperature-sensitive color-changing resin layer has a complete coloring point in a specific temperature range. The reversible / color-developable microcapsules are included, and the total light transmittance of the light-transmitting laminate is increased / decreased in gradation by decoloring / coloring the temperature-sensitive color-changing resin layer. [Selection] Figure 1

Description

  The present invention relates to a flexible light control sheet having light control properties due to changes in temperature. Specifically, lighting / blind windows for large membrane structures such as sports stadiums, lighting / blind windows for seat warehouses, lighting / blind windows for truck hoods, architectural curing sheets, ceiling membrane materials, space partition sheets, lighting / blinds for seat shutters Used for windows, store eaves tents, veranda awning sheets, etc., and the light transmission of the sheet is controlled by changes in temperature, especially when the surface temperature of the sheet ranges from 30 ° C to 70 ° C during the daytime. Decreases the rate in gradation to produce a light-shielding curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and increases the light transmittance in gradation in the evening when the temperature drops. The present invention relates to a light control sheet that can ensure daylighting and is excellent in weather resistance and flexibility.

  As dimming windows used in buildings, automobiles, ships, etc., Patent Documents 1 and 2 disclose that the temperature of the dimming panel of the multi-layer window body rises when sunlight is applied to the dimming panel of the multi-layer window body. As a result, the organic material solution becomes white turbid or colored to suppress light transmission, reduce the amount of direct solar radiation, and reduce the temperature of the light control panel by eliminating solar radiation, so that the organic material solution is in its original state Returning to the above, there has been disclosed a light control multi-layer window that stops the suppression of light transmission, incorporates sunlight, makes it easier to visually recognize the external space, and improves the feeling of release. These dimming multi-layer windows are made of a transparent plate-like body (glass) by encapsulating or microencapsulating at least two kinds of organic material solutions having different temperatures for suppressing light transmission by becoming clouded or colored. The light control function is obtained by changing the light transmittance twice or more by using the light control panel in a layered manner in the thickness direction of the light control panel. However, Patent Documents 1 and 2 are insufficient and unclear about an organic material solution that exhibits such a light control function, and a solution containing a water-soluble polymer compound, or a water-soluble polymer compound and a nonionic surfactant Or a solution containing a water-soluble polymer compound and a cloud point control substance, and the cloud point control substance is also described as an inorganic salt, an inorganic acid, an alkali, or an alcohol. Since there is no specific description, the invention of the light control multilayer window of Patent Documents 1 and 2 is not clear. Neither Patent Documents 1 and 2 are inventions that improve the weather resistance of an organic material solution that suppresses light transmission.

  Patent Document 3 is useful for heat ray reflective windows, dimming curtains, dimming partitions, projection screens, large-area reflective bulletin boards, traffic displays, and vehicle window materials, and can be heat-sealed at any position. A dimming layer (film) containing a dimming material composed of a thermochromic material or a photochromic material whose color developability is changed by stimulation as a dimming laminate that can be cut at the seal site via a heat seal layer A light control laminate having a laminated structure in which the film is held between (film) is disclosed. However, the invention of Patent Document 3 has the paragraph [0026] “Effect of the invention: The light-adhesive laminate of the present invention is heat-sealed by applying heat pressure at an arbitrary place. By cutting the portion, it is possible to perform cutting without exposing the cross section of the light control layer. ”From the description of“ a light control function, ”the light control laminate according to Patent Document 3 has a temperature rise or light. It is not clear what the purpose of use is to reduce the amount of transmitted light by coloring, or to increase the amount of transmitted light by increasing the temperature or erasing with light, and the effects in the examples are also unknown. is there. Therefore, it is unclear whether the thermochromic material described in Patent Document 3 is colored or decolored due to a temperature rise, and the photochromic material is also unclear. In addition, thermochromic materials and photochromic materials are unstable substances whose molecular structure changes upon stimulation, so that they are inferior in light resistance and are not intended to be used outdoors.

JP 07-238747 A JP 07-244300 A JP 2004-109582 A

  The present invention provides lighting / blind windows for large membrane structures such as sports stadiums, lighting / blind windows for seat warehouses, lighting / blind windows for truck hoods, architectural curing sheets, ceiling membrane materials, space partition sheets, and lighting / lighting for sheet shutters. Used for indoor and outdoor applications such as blind windows, store eaves tents, and veranda awning sheets, the light transmission of the sheet is controlled by changes in temperature, especially when the surface temperature of the sheet ranges from 30 ° C to 70 ° C during the day. The light transmittance of the main body is attenuated in gradation to produce a light-shielding curtain effect, thereby suppressing the internal air temperature by about 1 ° C. to 5 ° C., and in the evening when the temperature drops, the light transmittance is gradation It is intended to provide a light control sheet that can secure daylighting indoors and is excellent in weather resistance and flexibility.

  In order to solve the above-mentioned problems, in a light-transmitting laminate comprising a surface protective layer and a back surface resin layer and a temperature-sensitive color-changing resin layer in the middle, at least the surface protective layer is light semi-transmissive and UV-shielding When the temperature-sensitive color-changing resin layer contains reversible microcapsules that are decolored / colored, has a complete color development point in a specific temperature range, and the temperature of the light-transmitting laminate reaches the complete color development point, Color development of the thermochromic resin layer reduces the total light transmittance of the light transmissive laminate, and when the temperature of the light transmissive laminate falls below the complete color development point, the thermochromic resin layer is re-erased. The present invention has been completed by finding that the effect of increasing the total light transmittance of the light-transmitting laminate by color can be repeated according to changes in temperature.

  That is, the flexible light control sheet of the present invention is a light-transmitting laminate comprising a surface protective layer and a back resin layer, and a temperature-sensitive color-changing resin layer in the middle, at least the surface protective layer being a light Semi-transparent and UV-shielding, 1) a resin layer containing white fine particles and an ultraviolet absorber, or 2) a layer containing an ultraviolet absorber in an incompatible resin blend, wherein the temperature-sensitive color-changing resin layer is A reversible microcapsule for erasing / color development, the reversible microcapsule having a complete coloring point in any temperature range of 20 to 46 ° C., 47 to 55 ° C., and 56 ° C. or more, and transmitting the light When the temperature of the transparent laminate reaches the complete color development point, the total light transmittance of the light transmissive laminate (JIS K7375: 2008) is reduced by the color development of the thermochromic resin layer, and The temperature of the light transmissive laminate falls below the complete color point. When the it is preferable to increase the total light transmittance of the light transmitting laminates by decoloration of the thermochromic resin layer. This controls the light transmission of the sheet, and particularly when the surface temperature of the sheet reaches 30 ° C to 70 ° C during the daytime, the light transmittance of the sheet body is attenuated in a gradation, and the light shielding curtain effect is expressed. As a result, the internal temperature is kept low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmittance can be increased in gradation to ensure indoor lighting. Repeatable and drastically reduces the amount of UV light that passes through the temperature-sensitive color-changing resin layer, so the deterioration of the dye / developed compound-containing microcapsules over time (deterioration of reversibility of color development and decoloration, color development) The light control sheet which can be used outdoors can be obtained by the effect of suppressing deterioration of

  In the flexible light control sheet of the present invention, the temperature-sensitive color-changing resin layer includes two or three decolorable / color-reversible reversible microcapsules, and complete color development of the individual decolorizable / color-reversible microcapsules. The point difference is preferably 5 ° C. or more. As a result, the light transmittance of the sheet is controlled in a gradation in a wide range according to the temperature change, and particularly when the surface temperature of the sheet reaches 30 ° C. to 70 ° C. during the day, the light transmittance of the sheet body is adjusted in a gradation. Attenuating and producing a light-shielding curtain effect, so that the internal temperature is kept low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmittance can be increased in gradation to ensure indoor lighting. It becomes like this.

  In the flexible light-adjusting sheet of the present invention, the light-transmitting laminate includes a fabric, “surface protective layer / fabric / temperature-sensitive color changing resin layer / back surface resin layer”, “surface protective layer / temperature-sensitive color changing property”. Resin layer / fabric / back surface resin layer ”and“ surface protective layer / temperature-sensitive color-changing resin layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer ”. preferable. Light permeable laminates include fabrics that allow daylighting / blind windows in large membrane structures such as sports stadiums, daylighting / blind windows in seat warehouses, daylighting / blind windows in truck hoods, architectural curing sheets, ceiling membrane materials, spaces It is possible to obtain durable strength and dimensional stability suitable for use in industrial materials such as partition sheets, sheet shutter lighting / blind windows, store eaves tents, and veranda awning sheets.

  Since the flexible light control sheet of the present invention is excellent in weather resistance and flexibility, the lighting / blind window of a large membrane structure facility such as a sports stadium, the lighting / blind window of a sheet warehouse, the lighting / blind window of a truck hood, Suitable for use in industrial materials such as architectural curing sheets, ceiling membrane materials, space partition sheets, daylights / blind windows for sheet shutters, store eaves tents, and veranda awning sheets. According to this, the light transmittance of the sheet is controlled in gradation according to the temperature change, and particularly when the surface temperature of the sheet reaches 30 ° C. to 70 ° C. during the daytime, the light transmittance of the sheet body is attenuated in gradation. This produces a light-shielding curtain effect, which keeps the internal air temperature low by about 1 ° C to 5 ° C. Effect that the coercive can be repeatable in response to temperature change.

The figure which shows the cross section of the flexible light control sheet of this invention The figure which shows the cross section of the flexible light control sheet of this invention

  The flexible light control sheet of the present invention is a light transmissive laminate comprising a surface protective layer and a back surface resin layer, and a temperature-sensitive color-changing resin layer in the middle, at least the surface protective layer being light semi-transmissive, In addition, the light-transmissive laminate includes a fabric, and is “surface protective layer / fabric / temperature-sensitive color changing resin layer / back surface resin layer”, “surface protective layer / temperature-sensitive color changing resin layer / fabric”. / Back surface resin layer ”and“ surface protective layer / temperature-sensitive color-changing resin layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer ”.

  In the flexible light control sheet of the present invention, the resin used for the surface protective layer, the back surface resin layer, and the temperature-sensitive color-changing resin layer is vinyl chloride resin (containing a plasticizer), vinyl chloride copolymer resin, polyethylene resin. , Polypropylene resin, ethylene-vinyl acetate copolymer resin, blend of polypropylene resin and hydrogenated styrene copolymer resin, urethane resin, urethane elastomer, acrylic resin, acrylic elastomer, polyester elastomer, fluorine elastomer , Silicone elastomers and the like, and crosslinked thermoplastic resins and elastomers, and combinations thereof (blend or multilayer structure) can be used, but the surface protective layer, the back surface resin layer, and the temperature-sensitive color change The resin layer should be a composition of the same kind of resin. In a preferred. In particular, vinyl chloride resin (containing a plasticizer), polyethylene resin, polypropylene resin, urethane resin and the like are preferable in terms of versatility of the flexible light control sheet. Each of the surface protective layer, the back surface resin layer, and the temperature-sensitive color-changing resin layer is a film, sheet, and coating film formed by a calendar method, a T-die extrusion method, a casting method, a dipping method, or a coating method, and has a thickness of 0. 05 mm to 1.0 mm, preferably 0.1 mm to 0.5 mm is used.

  Both the front surface protective layer and the rear surface resin layer are preferably light semi-transmissive and ultraviolet shielding, but if at least the surface protective layer is light semi-transmissive and ultraviolet light shielding, the rear surface resin layer is not necessarily ultraviolet light. It is not necessary to have a shielding property, and it is not always necessary to have a semi-light-transmitting property. Since the temperature-sensitive color-changing resin layer whose hue is reversibly changed is intentionally covered and concealed by the light semi-transmissive surface protective layer and the back surface resin layer, This is a specification that is unlikely to be affected by hue changes in its appearance, and is essentially different from the conventional temperature-sensitive color-changing sheet that is characterized by hue changes in appearance. Accordingly, the light transmittance of the light control sheet of the present invention is controlled by the hue change of the temperature-sensitive color-changing resin layer, and is excellent in light resistance, so that it can be used outdoors. Although it is possible to control the light transmission only with this temperature-sensitive color-changing resin layer, it is not suitable for outdoor use because it has poor light resistance and reversible color change is lost in about several months. The light control sheet of the present invention is a semi-light-transmitting and UV-blocking surface protective layer (and a back surface resin layer) in order to stably maintain the light resistance of the temperature-sensitive color-changing resin layer for a long period of time. Concentrated on the layer to conceal the hue change of the thermochromic resin layer and focus on the light transmission control of the thermochromic resin layer, which has not been noticed so far, and the durability of the pot for outdoor use It is a thing.

  To make the surface protective layer and the back surface resin layer semi-transparent 1). Average particle diameter of titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, antimony oxide, barium sulfate, aluminum hydroxide, magnesium hydroxide, zinc borate, calcium carbonate, silica, kaolin, clay, talc, montmorillonite, etc. One or more kinds of light-diffusing spherical particles such as white fine particles of 05 μm to 5 μm, amorphous glass powder having an average particle diameter of 5 μm to 35 μm, glass beads, cross-linked acrylic resin beads, core-shell multilayer resin beads, and pearl pigments It is preferable to adjust the total light transmittance (JIS K7375: 2008) to 50 to 85% using a white to milky white coating film, film and sheet having a thickness of 0.1 mm to 0.5 mm. 2). Moreover, 0.1 to 0.5 mm white to milky white coating film, film having optical white turbidity (incompatible sea-island structure) by incompatible resin blend without including these white fine particles and the like, and The sheet may have a total light transmittance (JIS K7375: 2008) of 50 to 85%. Examples of incompatible combinations include vinyl chloride resin and polyethylene, vinyl chloride resin and polypropylene, vinyl chloride resin and polystyrene, vinyl chloride resin and silicone resin, vinyl chloride resin and fluorine-containing copolymer 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, acrylic resin and polycarbonate, polyamide and polystyrene, polyamide and polypropylene, etc. Mass ratio 25: The blend of 1-1: 25 can be illustrated.

  The surface protective layer and the back surface resin layer preferably contain 0.01 to 2% by mass of an organic ultraviolet absorber. Specifically, these include 2- (2H-benzotriazol-2-yl) -4,6- Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 6 -(2-benzotriazolyl) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, 2,2'-methylenebis [6- (2H-benzotriazole -2-yl) -4-t-octylphenol], 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] Benzotriazole compounds such as 2-2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-[(hexyl) oxy] phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4 , 6-Diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxy Examples thereof include phenol and triazine compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups. In addition, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) , And cyclic imino ester compounds such as 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 1,3-bis-[(2′-cyano-3 ′ , 3′-Diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy] methyl) propane, and 1,3-bis-[(2-cyano-3,3 Illustrative are cyanoacrylate compounds such as -diphenylacryloyl) oxy] benzene. In addition, as polymer-type UV absorbers, acrylic monomers and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid) having benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, etc. in the side chain And their derivatives, styrene, vinyl acetate, etc.) and those having a weight average molecular weight of 10,000 or more. Moreover, it is preferable that 0.1-5 mass% of inorganic type ultraviolet absorbers are included in a surface protective layer and a back surface resin layer, and these are specifically selected from titanium oxide, zinc oxide, cerium oxide, and iron oxide. The inorganic compound of a seed | species or more can be illustrated.

  The decolorizable / color-reversible reversible microcapsules contained in the temperature-sensitive color-changing resin layer include an electron-accepting compound selected from electron-donating color-forming organic compounds, gallic acid esters, and an organic medium as essential components. The electron-donating color-forming organic compounds include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans, and styrinoquinolines. And diazarhodamine lactones. Electron accepting compounds selected from gallate esters, benzoate esters and oxyphenols include dodecyl gallate, tridecyl gallate, tetradecyl gallate, pentadecyl gallate, hexadecyl gallate, octadecyl gallate, eicosyl gallate , Behenyl gallate, tetradecyl p-oxybenzoate, hexadecyl p-oxybenzoate, octadecyl p-oxybenzoate, behenyl p-oxybenzoate, tetradecyl 3,4-dihydroxybenzoate, tetradecyl m-oxybenzoate, p -Hexyloxyphenol, p-octyloxyphenol, p-decyloxyphenol, p-dodecyloxyphenol, etc. are exemplified, and the electron transfer reaction with the above-mentioned electron donating color-forming organic compound is alcohols, esters , Ketones, and is performed through an organic medium selected from hydrocarbons. The composition ratio of the electron-donating color-forming organic compound, the electron-accepting compound, and the organic medium is such that the electron-donating color-forming organic compound is 0.2 to 20 parts by mass with respect to 100 parts by mass of the organic medium. 10-80 mass parts of an active compound is preferable.

  Specific examples of the electron-donating color-forming organic compound include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl- 2-Methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl)- 4-azaphthalide, 3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluorane, -Methyl-6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- ( N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-anilino- 3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-xylidino-3-methyl-6-diethylaminofluorane, 1,2-benz-6 -Diethylaminofluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 1,2-benzen -6- (N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxystyryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ′ (3′H) isobenzofuran] -3′-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5 , 1 ′ (3′H) isobenzofuran] -3′-one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1) Benzopyrano (2,3-d) pyrimidine-5,1 ′ (3′H) isobenzofuran] -3′-one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2 , 3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino)- 4-methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino)- 8- (di-n-butylamino) -4-phenyl and the like can be mentioned, and these can be used in any combination.

  An example of a combination of an electron-donating color-forming organic compound, an electron-accepting compound, and an organic medium has a complete coloring point in a temperature range of 20 to 46 ° C .: 2- (di-n-butylamino) -8 -(Diventylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidin-5,1 '(3H) isobenzofuran] -3-one, stearyl gallate, stearic acid An example of a combination of n-heptyl / myristyl alcohol which turns colorless to pink at a complete color development temperature of 40 ° C. and gradually returns to colorless at a temperature below 40 ° C. 5 ′-[Ethyl (4-methylphenyl) amino]- 2 '-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9'-(9H) xanthen] -3-one, dodecyl gallate, cetyl caprate / myristyl An example of a combination of lecoles which exhibits a colorless to green color at a complete coloring temperature of 43 ° C. and gradually returns to colorless at a temperature lower than 43 ° C., 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1 -Ethyl-2-methylindol-3-yl) -4-azaphthalide, tetradecyl p-oxybenzoate, and tetradecyl alcohol, exhibit colorless to blue color at a complete coloring temperature of 42 ° C., and gradually decrease below 42 ° C. Example of returning to colorless, 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, p-octyloxyphenol / p -A combination of heptyloxyphenol and octadecane, which turns colorless to blue at a complete coloring temperature of 42 ° C and gradually returns to colorless at a temperature below 42 ° C. Examples include a combination of 3-dimethyl-6-diethylaminofluorane, p-hexyloxyphenol, and octadecane, which turns colorless to orange at a complete color development temperature of 40 ° C. and gradually returns to colorless at a temperature below 43 ° C. The mass ratio of the electron-donating color-forming organic compound, the electron-accepting compound, and the organic medium in these combinations is preferably about 1: 5 to 50: 5 to 50.

  Examples of combinations of electron-donating color-forming organic compounds, electron-accepting compounds, and organic media include those having a complete coloring point in a temperature range of 47 to 55 ° C .: 9-ethyl (3-methylbutyl) amino-spiro [ 12H-benzoxanthene-12,1 ′ (3′H) isobenzofuran] -3′-one, a combination of dodecyl gallate / stearyl gallate, heptyl stearate / docosane / lauryl alcohol, and colorless at a complete coloring temperature of 52 ° C. To red and gradually returns to colorless at temperatures below 52 ° C., 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindol-3-yl) Complete color temperature of 51 ° C. in combination of -4-azaphthalide, tetradecyl p-oxybenzoate / pentadecyl p-oxybenzoate, and octadecane Example of colorless to blue, gradually returning to colorless at temperatures below 51 ° C., in combination with 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, p-octyloxyphenol, and steryl caprate An example in which the color develops from colorless to pink at a complete color development temperature of 55 ° C., and gradually returns to colorless at a temperature lower than 55 ° C., and the like. The mass ratio of the organic medium is preferably about 1: 5 to 50: 5 to 50.

  An example of a combination of an electron-donating color-forming organic compound, an electron-accepting compound, and an organic medium has a complete coloring point in a temperature range of 56 ° C. or higher: 9-ethyl (3-methylbutyl) amino-spiro [12H -Benzoxanthen-12,1 '(3'H) isobenzofuran] -3'-one, tetradodecyl gallate, cetyl caprate / myristyl alcohol, which exhibits a colorless to red color at a complete coloring temperature of 60 ° C. Example of gradually returning to colorless at a temperature lower than 0 ° C., 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3 , 4-dihydroxybenzoate tetradecyl and octadecane, colorless to blue color at a complete color temperature of 64 ° C, and gradually disappeared at a temperature below 64 ° C. Example of returning to 1, a combination of 1,3-dimethyl-6-diethylaminofluorane, p-octyloxyphenol and hexadecyl alcohol, showing a colorless to orange color at a complete color development temperature of 62 ° C., and gradually decreasing below 62 ° C. An example of returning to colorless is given, and the mass ratio of the electron-donating color-forming organic compound, the electron-accepting compound, and the organic medium in these combinations is preferably about 1: 5 to 50: 5 to 50.

  For microencapsulation, any of known techniques such as coacervation method, interfacial polymerization method, in situ polymerization method, liquid curing coating method, air suspension coating method and spray drying method may be used. It is possible to obtain single-layer or multi-layer microcapsules having a particle size of 1 to 50 μm, which enclose the color developing organic compound, the electron-accepting compound, and the organic medium. Microcapsule shell wall is polyurea shell wall by polycondensation of polyamine and carbonyl compound, polyamide shell wall by polycondensation of polybasic acid chloride and polyamine, polyurethane by polycondensation of polyisocyanate and polyhydroxy compound Shell wall, polyester shell wall by polycondensation of polybasic acid chloride and polyhydroxy compound, epoxy resin shell wall by polycondensation of epoxy compound and polyamine, melamine resin shell wall by condensation of melamine / formalin prepolymer, urea Examples include urea resin shell walls by condensation of formalin prepolymers, but barrier shells in which components such as electron-donating colored organic compounds, electron-accepting compounds, and organic media that are encapsulated are not easily transferred out of the shell walls. Walls, shell walls with high heat resistance, shell walls with excellent weather resistance, etc. are preferred, especially epoxy resin shells , Melamine resin shell wall, the shell wall of thermosetting resins such as urea resin shell wall preferably.

  The temperature-sensitive color-changing resin layer contains two or three decolorable / color-reversible reversible microcapsules, and the complete color development points of the individual decolorizable / color-reversible microcapsules are different from each other by 5 ° C. or more, The light transmittance change of the obtained light control sheet can be controlled in two stages or three stages. The combination of two types of microcapsules is 20-46 ° C / 47-55 ° C, 20-46 ° C / 56 ° C or higher, 47-55 ° C / 56 ° C or higher, and the combination of three types of microcapsules is 20-46 ° C / It is 47-55 degreeC / 56 degreeC or more. In these combinations, the difference in complete color development point of each microcapsule is preferably 5 ° C. or more. If the difference between individual complete color development points is less than 10 ° C., the temperature range of dimming control may be narrowed. If the rate of temperature rise or fall is moderate, such as temperature fluctuations, the color change of color development or decoloration remains broad in each temperature zone at 5 to 20 ° C before and after the complete color development point, and the intensity change of each other is over. By wrapping, a gradation effect of light transmission can be obtained in a wide temperature range. Therefore, the light control sheet of the present invention does not define only those having a narrow color change temperature range and sharp color change. In addition, four or more kinds of microcapsules having coloring points in different temperature ranges can be used in combination, but the gradation change in light transmittance may not be much different from that in the case of using three kinds. The total amount of the decolorizable / color-reversible reversible microcapsules is 0.5 to 20% by mass, particularly 1 to 10% by mass, based on the temperature-sensitive color-changing resin layer.

  The flexible light-adjusting sheet of the present invention preferably contains a fabric as a core material for the purpose of dimensional stability of the light-controlling sheet, prevention of tearing breakage, etc., and the specifications are “surface protective layer / fabric / temperature-sensitive color change”. Resin layer / back surface resin layer ”,“ surface protective layer / temperature-sensitive color changing resin layer / fabric / back surface resin layer ”, and“ surface protective layer / temperature-sensitive color changing resin layer / fabric / temperature-sensitive color changing resin layer / back surface ” The design can be “resin layer” or the like. The cloth does not impair the light transmission, for example, the cloth itself is semi-translucent and has no light voids having a total light transmittance (JIS K7375: 2008) of 50 to 85%, or has a texture. If the fabric has a porosity of 1 to 10%, the fabric has a number of voids of 10 to 35% having a large number of voids in the texture, or a coarse fabric of a large porosity of 35 to 95% with a particularly wide gap between the yarns. Any of woven fabric, knitted fabric and non-woven fabric may be used. The woven fabric is a warp yarn group and a weft yarn group, and a plain woven fabric or a basket woven fabric (for example, a regular basket weave such as 2 × 2, 3 × 3, 4 × 4, 3 × 2, 4 × 2, 4 × 3, 2 × 3, 2 × 4, 3 × 4 etc. irregular basket weave), twill fabric (3 slashes, 4 slashes, 5 slashes, etc.), satin fabric (2 jumps, 3 Regular slats such as flying, 4 jumping, etc., and their changing fabrics, and also torn and weaving fabrics, mojiri fabrics (raised woven fabrics, woven fabrics), Russell knitted fabrics, lace knitted fabrics, etc., especially plain woven fabrics, 2 × 2 A basket fabric is preferable because of its excellent balance of physical properties. Further, it includes a warp yarn group, an upper right bias yarn group, and an upper left bias yarn group, such as a triaxial plain fabric, a triaxial basket fabric (for example, 2 × 2, 3 × 3), and the like. There is no limitation on the driving density of the warp and weft of the fabric (woven fabric) or the warp and bias yarn, and any driving density can be designed according to the thickness (denier) of the yarn used. These fabrics (woven fabrics) can be used with one or more known fiber treatments such as scouring, water repellent treatment, silane coupling agent treatment, organic titanate treatment, binder resin fixation, adhesive coating, etc. .

  A multifilament yarn, a short fiber spun yarn, and a monofilament yarn can be used as the warp and weft yarns forming the fabric. Particularly, the number of filaments is 30 to 300, and the fineness is 138 to 2223 dtex, preferably 277 to 1112 dtex. It is a multifilament yarn. The types of fibers are natural fibers such as kenaf and cotton (used as short fiber yarns), polypropylene, polyethylene, polyester (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc.), nylon, vinylon, acrylic, aromatic Synthetic fibers of polyester, aromatic polyamide, aromatic heterocyclic polymers (polyimidazole, polyoxazole, etc.), inorganic fibers such as glass, silica, basalt, alumina, boron, carbon, stainless steel, and the like Examples include mixed fibers and core-sheath fibers. In particular, the resistance to tearing breakage of the light control sheet main body obtained by using together the fiber yarns of aromatic polyester, aromatic polyamide, aromatic heterocyclic polymer and the like is enhanced. Moreover, fire resistance and a nonflammability can be provided to the light control sheet obtained by using the inorganic fiber thread | yarn by glass, a silica, a basalt, an alumina, carbon. In addition, water repellency treatment for preventing invasion of water from the cross-section of multifilament yarns by capillarity, and flameproofing treatment for providing self-extinguishing properties when flaming, or coating resin layer Adhesion treatment for improving the adhesiveness can be performed.

  The surface protective layer of the flexible light control sheet of the present invention is preferably provided with an antifouling layer. Examples of the antifouling layer include acrylic resins, fluorine-based copolymer resins, acrylic-silicon copolymer resins, and acrylic resins. Fluorine copolymer resins, acrylic-urethane copolymer resins, blends of acrylic resins and fluorine copolymer resins, and silica fine particles, colloidal silica, organosilicates, silane coupling agents, UV absorbers (paragraph [ 0016]) and the like. Examples of these antifouling layers are formed by applying and drying a resin solution soluble in a solvent or an emulsion in which a resin is dispersed in an aqueous dispersion medium by a coating method such as spray coating, gravure coating, or bar coating. This is a method in which a film having a fluorine-containing resin or a fluorine-containing copolymer resin as the outermost surface is laminated by an adhesive or heat melting. Further, it is possible to provide a photocatalyst layer containing a photocatalytic inorganic material (for example, photocatalytic titanium oxide, photocatalytic tungsten oxide, etc.) on these antifouling layers to prevent rain streak (dust) stains by hydrophilic self-cleaning. It is preferable. The antifouling layer of the flexible light control sheet of the present invention contains an appropriate amount of an antistatic agent (surfactant system, polymer heterocyclic polymer, conductive metal nanoparticles, etc.) in order to suppress dust adhesion. Can do.

  The flexible light control sheet (1) of the present invention will be described with reference to FIGS. FIG. 1 includes a fabric (2) as a base fabric, one side of which is coated with a temperature-sensitive color-changing resin layer (3), and further a surface protective layer (4) is coated on (3). FIG. 2 is a view showing an example of a cross section of the flexible light control sheet (1) in which the back surface is covered with a back surface resin layer (5). FIG. 2 includes the fabric (2) as a base fabric, and one surface thereof is a surface protective layer. A flexible light control sheet (1) coated with (4), the back surface of (2) is coated with a thermochromic resin layer (3), and further coated with a back surface resin layer (5) on (3) FIG.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In the following Examples and Comparative Examples, the light control effect by the test sheet was measured and evaluated by the following test method.
1) Dimming effect Total light transmittance (JIS K7375: 2008) is continuously measured with an integrating sphere color measuring device while raising a 10cm x 10cm square sheet piece from 20 to 80 ° C at a rate of 1 ° C / min. The change point (decoloring point) of the total light transmittance was determined.
2) Dimming effect after weathering test Outdoor exposure test (Soka City, Saitama: Expanding to 35 ° southward from May) Square of 10cm x 10cm from the stretch sheet after 3 months, 6 months and 1 year The sheet piece was collected, and the change point (decoloring point) of the total light transmittance was determined in the same manner as described above.

[Example 1]
As the fabric, a polyester multifilament plain fabric: (277 dtex × 277 dtex) / (12 / 25.4 mm × 13 / 25.4 mm), mass 65 g / m ² , porosity 31% was used.
Surface protective layer A soft vinyl chloride resin compound composition of the following formulation 1 is placed on a calender molding machine with a roll temperature of 180 to 190 ° C., and has a thickness of 0.12 mm and a total light transmittance (JIS K7375) of 66%. The film was used as a surface protective layer.
[Formulation 1] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flameproofing agent) 10 parts by weight Zinc oxide (white fine particles) ) 10 parts by mass benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass
Back surface resin layer A soft vinyl chloride resin compound composition of the following composition 2 is placed on a calender molding machine having a roll temperature of 180 to 190 ° C., and has a thickness of 0.12 mm and a total light transmittance (JIS K7375) of 77%. The film was a back resin layer.
[Formulation 2] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flame retardant) 10 parts by weight Antimony trioxide (flame retardant) Auxiliary agent) 1 part by mass benzotriazole-based compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol Cerium oxide (UV absorber) 0.2 parts by mass
Temperature-sensitive color-changing resin layer A soft vinyl chloride resin compound composition having the following composition 3 was placed on a calender molding machine having a roll temperature of 180 to 190 ° C., and light having a thickness of 0.15 mm and a total light transmittance (JIS K7375) of 64%. The semipermeable film was used as a temperature-sensitive color-changing resin layer.
[Formulation 3] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flame retardant) 10 parts by weight Antimony trioxide (flame retardant) Auxiliary agent) 1 part by mass benzotriazole-based compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass
Decolorable / color reversible microcapsules (1) 10 parts by mass * 3- [2-Ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindol-3-yl) -4 -Microcapsules of melamine resin shell wall (45% by mass) containing 5% by mass of azaphthalide, 25% by mass of tetradecyl p-oxybenzoate, and 25% by mass of tetradecyl alcohol (complete coloring temperature: 42 ° C .: colorless → Light blue → blue)
Light control sheet (1)
Using a laminator with a roll setting of 180 ° C., a 0.72 mm thick laminate sheet (1) having a “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” configuration was obtained. The transmission color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 25%, but at a temperature of 42 ° C. or higher, the change of colorless → light blue → blue was completed. The total light transmittance is limited to 13%, the sheet becomes colorless again at around room temperature, and the reversible dimming function that gradually expands the total light transmittance to 25% is developed. Reversible dimming function was maintained.

[Example 2]
Except for changing 10 parts by mass of the decolorable / color reversible microcapsule (1) of the thermosensitive color-changing resin layer (Formulation 3) of Example 1 to 10 parts by mass of the decolorable / color reversible microcapsule (2). As in Example 1, a 0.72 mm-thick laminate sheet (2) was obtained. The transmission color of the obtained sheet was colorless at room temperature and its total light transmittance (JIS K7375) was 26%, but at a temperature of 52 ° C. or higher, the change of colorless → light red → red was completed. The total light transmittance is limited to 10%, the sheet becomes colorless again at room temperature, and the reversible dimming function that gradually expands the total light transmittance to 26% is exhibited. Reversible dimming function was retained.
* Reversible erasable / decolorable microcapsules (2)
9-ethyl (3-methylbutyl) amino-spiro [12H-benzoxanthen-12,1 ′ (3′H) isobenzofuran] -3′-one 5 mass%, dodecyl gallate / stearyl gallate 25 mass% , A microcapsule of melamine resin shell wall (45% by mass) containing 25% by mass of heptyl stearate / docosane / lauryl alcohol (complete coloring temperature: 52 ° C .: colorless → light red → red)

[Example 3]
Except for changing 10 parts by mass of the decolorable / color reversible microcapsule (1) of the thermosensitive color-changing resin layer (Formulation 3) of Example 1 to 10 parts by mass of the decolorable / color reversible microcapsule (3). As in Example 1, a 0.72 mm thick laminate sheet (3) was obtained. The transmission color of the obtained sheet was colorless at room temperature and its total light transmittance (JIS K7375) was 27%, but at a temperature of 62 ° C. or higher, the change from colorless to light orange to orange was completed. , Its total light transmittance is limited to 12%, the sheet becomes colorless again at room temperature, and develops a reversible dimming function that gradually expands the total light transmittance to 27%. The same reversible dimming function was maintained.
* Reversible erasable / decolorable microcapsules (3)
Microcapsules of melamine resin shell wall (45% by mass) containing 5% by mass of 1,3-dimethyl-6-diethylaminofluorane, 25% by mass of p-octyloxyphenol, and 25% by mass of hexadecyl alcohol (completely Coloring temperature: 62 ° C: Colorless → Light orange → Orange

[Example 4]
A laminate sheet (4) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the temperature-sensitive color-changing resin layer (Formulation 3) in Example 1 was changed to the following Formulation 4. The transmission color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 26%, but at a temperature of 42 ° C. or higher, the change of colorless → light blue → blue was completed. The total light transmittance is limited to 16%, and at a temperature of 52 ° C or higher, the change from blue-violet to purple (blue of microcapsule (1) + red of microcapsule (2)) is completed, and the temperature of the sheet rises. As a result, the total light transmittance is limited in gradation from 26% to 10%. Next, as the temperature of the sheet decreases, the sheet again exhibits a blue-purple to blue color at a temperature around 42 ° C. Gradation reversible dimming function that the transmittance is gradually expanded to 16%, and the sheet exhibits blue → light blue → colorless again near normal temperature, and the total light transmittance is gradually expanded to 26%. And maintains the same reversible dimming function even after one year of outdoor exposure Was.
[Formulation 4] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flame retardant) 10 parts by weight Antimony trioxide (flame retardant) Auxiliary agent) 1 part by mass benzotriazole-based compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass
Decolorizable / color reversible microcapsules (1) 5 parts by mass
Decoloring / color development reversible microcapsule (2) 5 parts by mass

[Example 5]
A laminate sheet (5) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the temperature-sensitive color-changing resin layer (Formulation 3) in Example 1 was changed to the following Formulation 5. The transmission color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 25%, but at a temperature of 52 ° C. or higher, the change of colorless → light red → red was completed. The total light transmittance is limited to 15%, and at a temperature of 62 ° C or higher, the change from red to dark orange (red of microcapsule (2) + orange of microcapsule (3)) is completed, and the temperature of the sheet As the sheet temperature rises, its total light transmittance is limited in gradation from 25% to 7%. Next, as the sheet temperature falls, the sheet changes from dark orange to red again at a temperature around 52 ° C. The total light transmittance is gradually expanded to 15%, and the sheet is red → light red → colorless again at near normal temperature, and the total light transmittance gradually expands to 25%. Dimming function is exhibited and the same reversibility after one year of outdoor exposure The dimming function was maintained.
[Formulation 5] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flame retardant) 10 parts by weight Antimony trioxide (flame retardant) Auxiliary agent) 1 part by mass benzotriazole-based compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass
Decoloring / color development reversible microcapsule (2) 5 parts by mass
Decolorizable / color reversible microcapsule (3) 5 parts by mass

[Example 6]
A laminate sheet (6) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the temperature-sensitive color-changing resin layer (Formulation 3) in Example 1 was changed to the following Formulation 6. The transmission color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 24%, but at a temperature of 42 ° C. or higher, the change of colorless → light blue → blue was completed. The total light transmittance is limited to 18%, and at a temperature of 52 ° C. or higher, the change of blue → blue purple → purple (blue of microcapsule (1) + red of microcapsule (2)) is completed, and the total light transmission The rate is limited to 11% and the change from purple to dark purple (blue of microcapsule (1) + red of microcapsule (2) + orange of microcapsule (3)) is completed at a temperature of 62 ° C or higher. As the sheet temperature rises, its total light transmittance is limited in gradation from 24% to 6%, and then the sheet becomes dark purple again at a temperature around 52 ° C. as the sheet temperature falls. → Purple color and total light transmittance gradually increases to 11% Furthermore, at a temperature of 42 ° C. or less, the sheet again exhibits purple → blue-violet → blue, and the total light transmittance gradually expands to 18%. Further, near normal temperature, the sheet again exhibits blue → light blue → colorless. It exhibited a gradational reversible dimming function in which the total light transmittance gradually expanded to 24%, and retained the same reversible dimming function even after one year of outdoor exposure.
[Formulation 6] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flame retardant) 10 parts by weight Antimony trioxide (flame retardant) Auxiliary agent) 1 part by mass benzotriazole-based compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass
Decolorizable / color reversible microcapsules (1) 3 parts by mass
Decolorable / color reversible microcapsules (2) 4 parts by mass
Decoloring / color reversible microcapsules (3) 3 parts by mass

[Example 7]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 1 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. The laminated body sheet (7) which has the performance equivalent to was obtained.

[Example 8]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 2 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. The laminated body sheet (8) which has the performance equivalent to was obtained.

[Example 9]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 3 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. A laminate sheet (9) having the same performance as that of the above was obtained.

[Example 10]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 4 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. The laminated body sheet (10) which has the performance equivalent to was obtained.

[Example 11]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 5 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. To obtain a laminate sheet 11) having the same performance as the above.

[Example 12]
The configuration of “surface protective layer / temperature-sensitive color-changing resin layer / fabric / back surface resin layer” in Example 6 is referred to as “surface protection layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. A laminate sheet (12) having the same performance as that of the above was obtained.

[Examples 13 to 24]
The antifouling layer by the following [Formulation 7] is formed on the surface protective layer of each light control sheet obtained in Examples 1 to 12, and has the same performance as Examples 1 to 12, and further the antifouling layer Laminated body sheets (13) to (24) were obtained.
<Anti-fouling layer>
The light control sheets of Examples 1 to 12 were applied to a coating machine under 80 mesh gravure roll coating conditions, and coated with the antifouling composition of [Formulation 7] on the surface protective layer, and then heated in a 120 ° C hot air oven. An antifouling layer was provided by drying for 3 minutes.
[Formulation 7] Antifouling layer composition silica sol (particle size 20-30 nm: solid content 48% by mass) 100 parts by mass Vinyltriethoxysilane (silane coupling agent) 50 parts by mass Cerium oxide particles (particle size 15 nm: UV absorber) ) 5 parts by mass Polyethylene glycol type nonionic active agent (antistatic agent) 1 part by mass Diluent (water) 200 parts by mass

[Comparative Example 1]
A laminate sheet having a thickness of 0.6 mm and having a “temperature-sensitive color-changing resin layer / fabric / back surface resin layer” configuration as in Example 1 except that the surface protective layer is omitted from the light control sheet of Example 1. (25) was obtained. The obtained laminate sheet (25) exhibited a light control function similar to that of the light control sheet of Example 1. However, after 3 months of outdoor exposure from May to July, the color disappeared / colored. The reversible microcapsule (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light control function in which the light transmission color of the laminate sheet (25) was no longer changed was lost.

[Comparative Example 2]
A laminate sheet having a thickness of 0.6 mm and having a “temperature-sensitive color-changing resin layer / fabric / back surface resin layer” configuration as in Example 2, except that the surface protective layer was omitted from the light control sheet of Example 2. (26) was obtained. The obtained laminate sheet (26) exhibited a light control function similar to that of the light control sheet of Example 2, but after 3 months of outdoor exposure from May to July, the color disappearance / color development was observed. The reversible microcapsule (2) deteriorated and the red color exhibited at a temperature of 52 ° C. or more became colorless, and the light control function that no longer changes the light transmission color of the laminate sheet (26) was lost.

[Comparative Example 3]
A laminate sheet having a thickness of 0.6 mm and having a “temperature-sensitive color-changing resin layer / fabric / back surface resin layer” configuration as in Example 3, except that the surface protective layer is omitted from the light control sheet of Example 3. (27) was obtained. The obtained laminate sheet (27) exhibited a light control function similar to that of the light control sheet of Example 3. However, after 3 months of outdoor exposure from May to July, the color disappeared / colored. The reversible microcapsule (3) was deteriorated and the orange color exhibited at a temperature of 62 ° C. or higher became colorless, and the light control function in which the light transmission color of the laminate sheet (27) was no longer changed was lost.

[Comparative Example 4]
In the light control sheet of Example 1, 10 parts by mass of zinc oxide (white fine particles) was omitted from the soft vinyl chloride resin compound composition of the surface protective layer (formulation 1), and the total light transmittance of the surface protective layer was 93%. A laminate sheet (28) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the light transmissive film was used. The obtained laminate sheet (28) exhibited a light control function similar to that of the light control sheet of Example 1, but after 6 months of outdoor exposure from May to October, the color disappeared / colored. The reversible microcapsule (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light control function in which the light transmission color of the laminate sheet (28) no longer changed was lost.

[Comparative Example 5]
In the light control sheet of Example 1, 0.2 parts by mass of a benzotriazole-based compound (ultraviolet absorber) from the soft vinyl chloride resin compound composition of the surface protective layer (formulation 1), and cerium oxide (ultraviolet absorber) 0. A laminate sheet (29) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that 4 parts by mass were omitted and a light semi-transmissive film having a total light transmittance of 66% was used as the surface protective layer. The obtained laminate sheet (29) exhibited a light control function similar to that of the light control sheet of Example 1, but after 6 months of outdoor exposure from May to October, the color disappearance / color development was observed. The reversible microcapsule (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light control function that no longer changes the light transmission color of the laminate sheet (29) was lost.

[Example 25]
The surface protective layer of Example 1 was changed to a soft vinyl chloride resin compound composition (incompatible resin blend cloudy system with silicon elastomer) according to the following formulation 8, thickness 0.12 mm, total light transmittance (JIS K7375) A laminate sheet (30) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that a 71% light translucent film was used. The light control function of the obtained sheet was equivalent to that of the laminate sheet (1), and had the same reversible light control function even after one year of outdoor exposure.
[Formulation 8] Soft vinyl chloride resin compound composition Suspension polymerization polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamol DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight Aromatic phosphate ester (flameproofing agent) 10 parts by weight Silicone elastomer 10 parts by weight Benzo Triazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol cerium oxide (ultraviolet absorber) 0.4 parts by mass

[Example 26]
A laminate sheet (31) having a thickness of 0.72 mm was obtained in the same manner as in Example 2 except that the surface protective layer in Example 2 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (2), and had the same reversible light control function even after one year of outdoor exposure.

[Example 27]
A laminate sheet (32) having a thickness of 0.72 mm was obtained in the same manner as in Example 3 except that the surface protective layer in Example 3 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (3), and had the same reversible light control function even after one year of outdoor exposure.

[Example 28]
A laminate sheet (33) having a thickness of 0.72 mm was obtained in the same manner as in Example 4 except that the surface protective layer in Example 4 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (4), and had the same reversible light control function even after one year of outdoor exposure.

[Example 29]
A laminate sheet (34) having a thickness of 0.72 mm was obtained in the same manner as in Example 5 except that the surface protective layer in Example 5 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (5) and had the same reversible light control function even after one year of outdoor exposure.

[Example 30]
A laminate sheet (35) having a thickness of 0.72 mm was obtained in the same manner as in Example 6 except that the surface protective layer in Example 6 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (6) and had the same reversible light control function even after one year of outdoor exposure.

[Example 31]
A laminate sheet (36) having a thickness of 0.72 mm was obtained in the same manner as in Example 7, except that the surface protective layer in Example 7 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (7), and had the same reversible light control function even after one year of outdoor exposure.

[Example 32]
A laminate sheet (37) having a thickness of 0.72 mm was obtained in the same manner as in Example 8, except that the surface protective layer in Example 8 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (8), and had the same reversible light control function even after 1 year of outdoor exposure.

[Example 33]
A laminate sheet (38) having a thickness of 0.72 mm was obtained in the same manner as in Example 9, except that the surface protective layer in Example 9 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (9), and had the same reversible light control function even after one year of outdoor exposure.

[Example 34]
A laminate sheet (39) having a thickness of 0.72 mm was obtained in the same manner as in Example 10 except that the surface protective layer in Example 10 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (10), and had the same reversible light control function even after one year of outdoor exposure.

[Example 35]
A laminate sheet (40) having a thickness of 0.72 mm was obtained in the same manner as in Example 11 except that the surface protective layer in Example 11 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (11), and had the same reversible light control function even after one year of outdoor exposure.

[Example 36]
A laminate sheet (41) having a thickness of 0.72 mm was obtained in the same manner as in Example 12 except that the surface protective layer in Example 12 was replaced with the surface protective layer in Example 25. The light control function of the obtained sheet was equivalent to that of the laminate sheet (12), and had the same reversible light control function even after one year of outdoor exposure.

[Examples 37 to 48]
An antifouling layer according to [Formulation 7] is formed on the surface protective layer of each light control sheet obtained in Examples 25 to 36, and an antifouling layer is additionally provided with the same performance as in Examples 25 to 36. Laminate sheets (42) to (53) were obtained.

  In the flexible light control sheet of the present invention, the light transmittance of the sheet is controlled in gradation by the temperature change, and particularly when the surface temperature of the sheet reaches 30 ° C. to 70 ° C. during the daytime, the light transmission of the sheet main body is achieved. Decreases the rate in gradation to produce a light-shielding curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and increases the light transmittance in gradation in the evening when the temperature drops. The effect of ensuring daylighting can be repeated according to changes in temperature, and it has excellent weather resistance and flexibility. Therefore, lighting / blind windows for large membrane structures such as sports stadiums, and lighting / blind windows for seat warehouses. , Truck hood lighting / blind windows, architectural curing sheets, ceiling membrane materials, space partition sheets, sheet shutter lighting / blind windows, store eaves tents, veranda awning sheets, etc. It is suitable for use in industrial materials.

1: Flexible light control sheet 2: Fabric 3: Temperature-sensitive color-changing resin layer 4: Surface protective layer 5: Back surface resin layer

Claims (3)

  A light-transmitting laminate comprising a surface protective layer and a back surface resin layer, and a temperature-sensitive color-changing resin layer between them, wherein at least the surface protective layer is light semi-transmissive and UV-shielding 1) A resin layer containing white fine particles and an ultraviolet absorber, or 2) a layer containing an ultraviolet absorber in an incompatible resin blend, wherein the temperature-sensitive color-changing resin layer comprises a decolorable / color reversible microcapsule The reversible microcapsule has a complete color development point in any temperature range of 20 to 46 ° C., 47 to 55 ° C., and 56 ° C. or more, and the temperature of the light-transmitting laminate is the complete color development point. When it reaches, the total light transmittance (JIS K7375: 2008) of the light-transmitting laminate is reduced by the color development of the thermochromic resin layer, and the temperature of the light-transmitting laminate is the complete color development. When the temperature drops below the point, the temperature-sensitive color-changing resin layer Flexible light control sheet, characterized in that to increase the total light transmittance of the light transmitting laminate by color.   The temperature-sensitive color-changing resin layer contains two or three decolorable / color-reversible reversible microcapsules, and the difference between the complete color development points of the individual decolorizable / color-reversible microcapsules is 5 ° C. or more. 2. The flexible light control sheet according to 1.   The light-transmitting laminate includes a fabric, “surface protective layer / fabric / temperature-sensitive color changing resin layer / back surface resin layer”, “surface protective layer / temperature-sensitive color changing resin layer / fabric / back surface resin layer”, and 3. The flexible light control according to claim 1, wherein the dimming structure is any one selected from “surface protective layer / temperature-sensitive color-changing resin layer / fabric / temperature-sensitive color-changing resin layer / back surface resin layer”. Sheet.