JP6771209B2 - Flexible dimming sheet - Google Patents

Description

The present invention relates to a flexible dimming sheet having dimmability due to changes in temperature. For details, see the lighting / blind windows of large membrane structure facilities such as sports stadiums, the lighting / blind windows of seat warehouses, the lighting / blind windows of truck hoods, building curing sheets, ceiling film materials, space partition sheets, and seat shutter lighting / blinds. It is used for windows, store eaves tents, balcony awning sheets, etc., and the light transmission of the sheet is controlled by temperature changes. Especially when the surface temperature of the sheet reaches 30 ° C to 70 ° C during the daytime, the light transmission of the sheet body The rate is gradually attenuated to create a blackout curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmission rate is gradually increased indoors. The present invention relates to a light control sheet that can secure daylighting and is excellent in weather resistance and flexibility.

As dimming windows used in buildings, automobiles, ships, etc., Patent Documents 1 and 2 describe that the temperature of the dimming panel of the multi-layer window body rises when the dimming panel of the multi-layer window body is exposed to sunlight. As a result, the organic material solution becomes cloudy or colored to suppress light transmission, reducing the amount of direct sunlight, and the temperature of the dimming panel is lowered by the absence of sunlight, so that the organic material solution is in its original state. The invention of a dimming multi-layer window that stops the suppression of light transmission, takes in sunlight, makes it easier to see the external space, and improves the feeling of liberation is disclosed. These dimming multi-layer windows are each encapsulated in a film, microencapsulated, or a transparent plate-like body (glass) of at least two or more kinds of organic material solutions having different temperatures of whitening or coloring to suppress light transmission. It is a device that obtains a dimming function by sandwiching it between plates and resin plates) and using it in layers in the thickness direction of the dimming panel so that the light transmittance changes twice or more. However, Patent Documents 1 and 2 lack and are unclear about the organic material solution that exhibits such a dimming function, and are a solution containing a water-soluble polymer compound, or a water-soluble polymer compound and a nonionic surfactant. It is described as a solution containing water-soluble polymer compound and a cloud point control substance, and the cloud point control substance is also described only as inorganic salts, inorganic acids, alkalis, and alcohols, and is also described in Examples. Since there is no specific description, the invention of the dimming multilayer window of Patent Documents 1 and 2 is not clear. Further, neither Patent Documents 1 and 2 are inventions for improving the weather resistance of an organic material solution that suppresses light transmission.

Further, Patent Document 3 is useful for heat ray reflecting windows, dimming curtains, dimming partitions, projection screens, large area reflective bulletin boards, traffic displays, vehicle window materials, heat sealing is possible at any position, and heat is provided. As a dimming laminate that can be cut at the sealing site, a dimming layer (film) containing a dimming material made of a thermochromic material or a photochromic material that changes color development by stimulation is formed on a substrate via a heat sealing layer. A dimming laminate having a laminated structure in which the film is held between the (films) is disclosed. However, the invention of Patent Document 3 describes in paragraph [0026] "Effect of the invention: In the dimming laminate of the present invention, the heat sealing material is heat-sealed by applying heat pressure at an arbitrary place, so that the heat-sealing material is heat-sealed. From the description of "By cutting the portion, the cutting process can be performed without exposing the cross section of the dimming layer." Since the invention is not related to the dimming function, the dimming laminate according to Patent Document 3 has a temperature rise or light. It is not clear whether it is colored with to reduce the amount of light transmission, or it is intended to increase the amount of light transmission by increasing the temperature or decoloring with light, and the effect of action in the examples is also unknown. is there. Therefore, it is unknown whether the thermochromic material described in Patent Document 3 is colored or decolorized by increasing the temperature, and the photochromic material is also unknown. Further, the thermochromic material and the photochromic material are inferior in light resistance because they are unstable substances whose molecular structure changes with a stimulus, and they are not intended to be used outdoors.

Japanese Unexamined Patent Publication No. 07-238747 Japanese Unexamined Patent Publication No. 07-244300 Japanese Unexamined Patent Publication No. 2004-109582

The present invention provides daylighting / blind windows for large membrane structure facilities such as sports stadiums, daylighting / blind windows for seat warehouses, daylighting / blind windows for truck hoods, building curing sheets, ceiling film materials, space partition sheets, and daylighting for seat shutters. It is 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 temperature changes, especially when the surface temperature of the sheet reaches 30 ° C to 70 ° C during the daytime. The light transmission rate of the main body is attenuated in a gradation to create a light-shielding curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and the light transmission rate is gradation in the evening when the temperature drops. By raising the light, it is possible to secure indoor lighting, and it is intended to provide a dimming sheet having excellent weather resistance and flexibility.

In order to solve the above problems, in a light-transmitting laminate including a front surface protective layer and a back surface resin layer and a temperature-sensitive discoloration resin layer in the middle, at least the surface protective layer is semi-transmissive and shields ultraviolet rays. When the temperature-sensitive color-changing resin layer contains reversible microcapsules for decolorization / color development, has a perfect color development point in a specific temperature range, and the temperature of the light-transmitting laminate reaches the perfect color development point. The 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 drops below the complete color development point, the thermochromic resin layer is re-erased. We have found that the action of increasing the total light transmittance of the light-transmitting laminate depending on the color can be repeated in response to changes in temperature, and have completed the present invention.

That is, the flexible light control sheet of the present invention is a light-transmitting laminate including a front surface protective layer and a back surface resin layer, and a temperature-sensitive discoloration resin layer in the middle, and at least the surface protective layer is light. It is semi-transmissive and UV-shielding, and is 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 discoloration resin layer is includes a reversible microcapsules decoloring / color, this reversibility microcapsules, 30 -46 ° C., has a 47-55 ° C., and full color point in any of the temperature zones of 56 ° C. or more, the light transmission When the temperature of the sex laminate reaches the perfect color development point, the color of the thermochromic resin layer reduces the total light transmittance (JIS K7375: 2008) of the light-transmitting laminate, and the above-mentioned When the temperature of the light-transmitting laminate drops below the complete color-developing point, it is preferable to increase the total light transmittance of the light-transmitting laminate by decolorizing the temperature-sensitive discoloration resin layer. As a result, the light transmittance of the sheet is controlled, and especially 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 manner to exhibit a light-shielding curtain effect. 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 is increased in a gradational manner to ensure indoor lighting, and its action and effect respond to changes in temperature. Since it is repeatable and the amount of ultraviolet rays transmitted through the thermochromic resin layer is significantly reduced, the microcapsules containing dye / color-developing compounds deteriorate over time due to ultraviolet rays (deterioration of reversibility of color development and decolorization, color development). A dimming sheet that can be used outdoors can be obtained due to the effect of suppressing deterioration of the light.

In the flexible light control sheet of the present invention, the temperature-sensitive discoloration resin layer contains two or three types of decolorizing / coloring reversible microcapsules, and the complete color development of each decolorizing / coloring reversible microcapsules. The point difference is preferably 5 ° C. or higher. As a result, the light transmittance of the sheet is controlled in a wide range and gradation by the temperature change, and especially when the surface temperature of the sheet reaches 30 ° C to 70 ° C during the daytime, the light transmittance of the sheet body is gradationally controlled. By attenuating and exhibiting a blackout curtain effect, the internal temperature is kept low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmittance is gradually increased to ensure indoor lighting. Will be.

In the flexible dimming sheet of the present invention, the light-transmitting laminate contains a cloth, and is "front surface protective layer / cloth / thermosetting resin layer / back surface resin layer" and "surface protective layer / thermosetting. Any one of the configurations selected from "resin layer / fabric / back surface resin layer" and "front surface protective layer / thermosetting resin layer / fabric / thermosetting resin layer / back surface resin layer". preferable. By including the fabric in the light-transmitting laminate, the lighting / blind windows of large membrane structure facilities such as sports stadiums, the lighting / blind windows of the seat warehouse, the lighting / blind windows of the truck hood, the building curing sheet, the ceiling film material, and the space. It is possible to obtain durable strength and dimensional stability suitable for use in industrial materials such as partition sheets, daylighting / blind windows of sheet shutters, store eaves tents, and veranda awning sheets.

Since the flexible dimming sheet of the present invention has excellent weather resistance and flexibility, daylighting / blind windows of large membrane structure facilities such as sports stadiums, daylighting / blind windows of seat warehouses, daylighting / blind windows of truck hoods, etc. Suitable for use in industrial materials such as building curing sheets, ceiling film materials, space partition sheets, daylighting / blind windows for sheet shutters, store eaves tents, veranda awning sheets, etc., for use of the flexible dimming sheet of the present invention. According to this, the light transmittance of the sheet is controlled gradationally by the temperature change, and especially when the surface temperature of the sheet reaches 30 ° C. to 70 ° C. during the daytime, the light transmittance of the sheet body is gradationally attenuated. It exerts a light-shielding curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmission rate is increased in gradation to ensure indoor lighting. The effect can be repeated according to changes in temperature.

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-transmitting laminate including a front surface protective layer and a back surface resin layer, and a temperature-sensitive discoloration resin layer in the middle, and at least the surface protective layer is semi-transmissive. In addition, it is UV-shielding and the light-transmitting laminate contains the cloth, which includes "front surface protective layer / cloth / temperature-sensitive color-sensitive resin layer / back surface resin layer" and "surface protection layer / temperature-sensitive color-sensitive resin layer / cloth". It has one of the configurations of "/ back surface resin layer" and "front surface protective layer / temperature-sensitive color-changing resin layer / fabric / temperature-sensitive color-sensitive resin layer / back surface resin layer".

In the flexible light control sheet of the present invention, the resins used for the front surface protective layer, the back surface resin layer, and the temperature-sensitive discoloration resin layer are vinyl chloride resin (containing a plasticizer), vinyl chloride-based copolymer resin, and polyethylene resin. , Polypropylene resin, Ethylene-vinyl acetate copolymer resin, Blend of polypropylene resin and hydrogenated styrene-based copolymer resin, Urethane resin, Urethane-based elastomer, Acrylic resin, Acrylic-based elastomer, Polyester-based elastomer, Fluorine-based elastomer , Silicon-based elastomers, and cross-linked bodies of these thermoplastic resins and elastomers, and their combined use (blend or multi-layer structure), etc., but the front surface protective layer, back surface resin layer, and temperature-sensitive discoloration It is preferable that the resin layer is a composition made of the same type of resin from the viewpoint of melt adhesion between the interfaces of each layer. 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 layer of the front surface protective layer, the back surface resin layer, and the thermosetting resin layer is a film, sheet, or coating film obtained 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 back surface resin layer are preferably light semitransparent and ultraviolet shielding property, but if at least the front surface protective layer is light semitransmissive and ultraviolet shielding property, the back surface resin layer is not necessarily ultraviolet ray. It does not have to have a shielding property, and does not necessarily have to have a translucent light. The flexible light control sheet of the present invention is a light control sheet because the temperature-sensitive color-changing resin layer whose hue changes reversibly is intentionally covered and concealed by a light semitransparent front surface protective layer and a back surface resin layer. The specifications are such that the appearance of the sheet is not easily affected by the change in hue, and the specifications are essentially different from those of the conventional temperature-sensitive color-changing sheet, which is characterized by the change in hue of the appearance. Therefore, the light transmittance of the light control sheet of the present invention is controlled by the hue change of the thermosetting resin layer, and it has excellent light resistance, so that it can be used outdoors. Although it is possible to control the light transmission only with this thermosetting resin layer, it is not suitable for outdoor use because the light resistance is poor and the reversible discoloration is impaired in about several months. In the light control sheet of the present invention, in order to maintain the light resistance of the thermosetting resin layer stably for a long period of time, the surface protective layer (and the back surface resin layer) that is translucent and UV-shielding is a thermosetting resin. It is provided on the layer to conceal the hue change of the thermosetting resin layer, focusing on the light transmission control of the thermosetting resin layer, which has not been noticed until now, and the durability of the pot life for outdoor use. It was done.

To make the front surface protective layer and the back surface resin layer semitransparent to light, 1). Average particle size 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, and montmorillonite. One or more types of white fine particles of 05 μm to 5 μm, light-diffusing spherical particles such as irregular glass powder with an average particle diameter of 5 μm to 35 μm, glass beads, crosslinked acrylic resin beads, core-shell multilayer resin beads, and pearl pigments. It is preferable to use and adjust the total light transmittance (JIS K7375: 2008) of white to milky white coatings, films and sheets having a thickness of 0.1 mm to 0.5 mm to 50 to 85%. 2). In addition, 0.1 mm to 0.5 mm white to opalescent coating films, films and films that do not contain these white fine particles and utilize optical white turbidity (incompatible sea island structure) due to an incompatible resin blend. 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, and polystyrene. And polypropylene, urethane resin and polyethylene, urethane resin and polypropylene, polyester resin and polyethylene, polyester resin and polypropylene, polyamide and polypropylene, acrylic resin and polystyrene, acrylic resin and polycarbonate, polyamide and polystyrene, polyamide and polypropylene, etc., mass ratio 25: An example is a blend of 1 to 1:25.

The front surface protective layer and the back surface resin layer preferably contain 0.01 to 2% by mass of an organic ultraviolet absorber, and specifically, these are 2- (2H-benzotriazole-2-yl) -4,6- Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-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-benzotriazole-2-yl) phenol] , 2-2'-Methylenebis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol and other benzotriazole compounds, 2- (4,6-diphenyl-1,3) 5-Triazine-2-yl) -5-[(hexyl) oxy] phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2-( 4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyl Examples thereof include oxyphenol and triazine-based compounds such as 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified. In addition, 2,2'-p-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine-4-one) , And cyclic iminoester compounds such as 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-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) −Diphenylacryloyl) Oxygen] Cyanoacrylate compounds such as benzene are exemplified. Further, as a polymer type ultraviolet absorber, an acrylic monomer having a benzophenone compound, a benzotriazole compound, a triazine compound, a cyanoacrylate compound or the like in a side chain and another ethylene unsaturated compound (acrylic acid, methacrylic acid) And their derivatives, styrene, vinyl acetate, etc.) and those having a weight average molecular weight of 10,000 or more can be exemplified. Further, the front surface protective layer and the back surface resin layer preferably contain 0.1 to 5% by mass of an inorganic ultraviolet absorber, and these are specifically selected from titanium oxide, zinc oxide, cerium oxide, and iron oxide. Inorganic compounds of more than one species can be exemplified.

The decolorizing / color-developing reversible microcapsules contained in the thermochromic resin layer contain an electron-donating color-developing organic compound, an electron-accepting compound selected from galvanic acid esters, and an organic medium as essential components. As electron-donating color-forming organic compounds, diphenylmethanephthalides, phenylindrillphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindrillazaphthalides, fluorans, and stirinoquinolins are used. , Diazarodamine lactones and the like. Examples of the electron-accepting compound selected from gallic acid esters, benzoic acid esters and oxyphenols include gallic acid dodecyl, gallic acid tridecyl, gallic acid tetradecyl, gallic acid pentadecyl, gallic acid hexadecyl, gallic acid octadecyl and gallic acid eicosyl. , Gallic acid gallic acid, tetradecyl p-oxybenzoate, hexadecyl p-oxybenzoate, octadecyl p-oxybenzoate, behenyl p-oxybenzoate, tetradecyl 3,4-dihydroxybenzoate, tetradecyl m-oxybenzoate, p Examples thereof include −hexyloxyphenol, p-octyloxyphenol, p-decyloxyphenol, p-dodecyloxyphenol, etc., and the electron transfer reaction with the electron-donating color-forming organic compound is performed on alcohols, esters, etc. It is carried out via an organic medium selected from ketones and hydrocarbons. The composition ratio of the electron-donating color-forming organic compound, the electron-accepting compound, and the organic medium is 0.2 to 20 parts by mass of the electron-donating color-forming organic compound with respect to 100 parts by mass of the organic medium. The sex compound is preferably 10 to 80 parts by mass.

Specific examples of the electron-donating color-developing organic compound include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide and 3- (4-diethylaminophenyl) -3- (1-ethyl-). 2-Methylindole-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl)- 4-Azaphthalide, 3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 2-methyl-6- (N-ethyl-N-p-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylamino Fluolane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N-methylanilino) -6- (N-Ethyl-N-p-Tolylamino) Butyl, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-diethylamino Fluolane, 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-benz-6- (N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxy) Styryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidin-5,1'(3'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-Methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidin-5,1'(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (Di-n-butylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidin-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-N-i-amylamino)- 4-Methyl-spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran] -3'-on, 2- (di-n-butylamino)- Examples thereof include 8- (di-n-butylamino) -4-phenyl, which can be used in any plurality of combinations.

As an example of a combination of an electron-donating color-forming organic compound, an electron-accepting compound, and an organic medium, those having a perfect color-developing point in the 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 that changes from 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]- A combination of 2'-(methylphenylamino) -spiro [isobenzofuran-1 (3H), 9'-(9H) xanthene] -3-one, dodecyl carpentate, cetyl caprate / myristyl alcohol, complete color development temperature 43 An example in which the substance changes from colorless to green at ° C and gradually returns to colorless at a temperature below 43 ° C, 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindole-3). -Il) -4-Azaphthalide, tetradecyl p-oxybenzoate, and tetradecyl alcohol change from colorless to blue at a complete color development temperature of 42 ° C, and gradually return to colorless at temperatures below 42 ° C. 2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, p-octyloxyphenol / p-heptyloxyphenol, octadecane An example in which the color changes from colorless to blue at a complete color development temperature of 42 ° C and gradually returns to colorless at a temperature below 42 ° C. Complete with a combination of 1,3-dimethyl-6-diethylaminofluorane, p-hexyloxyphenol, and octadecane. Examples thereof include an example in which the color changes from colorless to orange at a color development temperature of 40 ° C. and gradually returns to colorless at a temperature below 43 ° C., and electron-donating color-forming organic compounds, electron-accepting compounds, and organic media in these combinations. The mass ratio of is preferably about 1: 5 to 50: 5 to 50.

As an example of a combination of an electron-donating color-developing organic compound, an electron-accepting compound, and an organic medium, those having a perfect coloring point in the temperature range of 47 to 55 ° C.: 9-ethyl (3-methylbutyl) amino-spiro [ 12H-benzoxanthene-12,1'(3'H) isobenzofuran] -3'-one, dodecyl benzoate / stearyl benzoate, heptyl stearate / docosan / lauryl alcohol, colorless at a complete color development temperature of 52 ° C. 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindole-3-yl), an example in which the compound turns red and gradually returns to colorless at a temperature below 52 ° C. A combination of -4-azaphthalide, tetradecyl p-oxybenzoate / pentadecyl p-oxybenzoate, and octadecane, which changes from colorless to blue at a complete color development temperature of 51 ° C and gradually returns to colorless at temperatures below 51 ° C. , 2-Benzu 6- (N-ethyl-N-isobutylamino) fluorane, p-octyloxyphenol, steryl caprate, which changes from colorless to pink at a complete color development temperature of 55 ° C and at temperatures below 55 ° C. Examples thereof include examples in which the compound gradually returns to colorless, and the mass ratio of the electron-donating color-developing organic compound, the electron-accepting compound, and the organic medium in these combinations is preferably about 1: 5 to 50: 5 to 50.

As an example of a combination of an electron-donating color-developing organic compound, an electron-accepting compound, and an organic medium, those having a perfect coloring point in a temperature range of 56 ° C. or higher: 9-ethyl (3-methylbutyl) amino-spiro [12H -Benzoxanthene-12,1'(3'H) isobenzofuran] -3'-one, tetradodecyl gallic acid, cetyl caprate / myristyl alcohol, which turns colorless to red at a complete color development temperature of 60 ° C, 60 Examples of gradually returning to colorless at temperatures below ° C., 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3 , A combination of tetradecyl 4-dihydroxybenzoate and octadecane, which changes from colorless to blue at a complete color development temperature of 64 ° C and gradually returns to colorless at temperatures below 64 ° C, 1,3-dimethyl-6-diethylaminofluorane, Examples include a combination of p-octyloxyphenol and hexadecyl alcohol, which changes from colorless to orange at a complete color development temperature of 62 ° C. and gradually returns to colorless at a temperature below 62 ° C., and the electron donating property in these combinations. The mass ratio of the color-developing organic compound, the electron-accepting compound, and the organic medium is preferably about 1: 5 to 50: 5 to 50.

The microencapsulation may be performed by any of known techniques such as a core selvation method, an interfacial polymerization method, an in situ polymerization method, a submerged curing coating method, an aerial suspension coating method, and a spray drying method, and electron donation is performed by these methods. It is possible to obtain single-layer or multi-layer microcapsules having a particle size of 1 to 50 μm containing a sex-forming organic compound, an electron-accepting compound, and an organic medium. The shell wall of the microcapsule is a polyurea shell wall by polycondensation of polyvalent amine and carbonyl compound, polyamide shell wall by polycondensation of polybasic acid chloride and polyvalent amine, and polyurethane by polycondensation of polyvalent isocyanate 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 polyvalent amine, melamine resin shell wall by condensation of melamine / formarin prepolymer, urea / A urea resin shell wall formed by condensation of a formalin prepolymer can be exemplified, but a barrier shell in which components such as an electron-donating color-forming organic compound, an electron-accepting compound, and an organic medium contained therein are difficult to be transferred to the outside of the shell wall and discharged. A wall, a shell wall having high heat resistance, a shell wall having excellent weather resistance, and the like are preferable, and a shell wall made of a thermocurable resin such as an epoxy resin shell wall, a melamine resin shell wall, and a urea resin shell wall is particularly preferable.

The thermochromic resin layer contains 2 or 3 types of decolorizing / coloring reversible microcapsules, and the complete color development points of the individual decolorizing / coloring reversible microcapsules are different from each other by 5 ° C. or more. The change in light transmittance of the obtained light control sheet can be controlled in two steps or three steps. The combination of two types of microcapsules is 20 to 46 ° C / 47 to 55 ° C, 20 to 46 ° C / 56 ° C or higher, and the combination of three types of microcapsules is 20 to 46 ° C / It is 47 to 55 ° C./56 ° C. or higher. In these combinations, the difference in the complete color development points of the individual microcapsules is preferably 5 ° C. or higher. If the difference between the individual perfect color development points is less than 10 ° C., the temperature range of the dimming control may be narrowed. If the rate of temperature rise or fall is gradual like temperature fluctuations, the shade change of color development or decolorization remains broad in each temperature zone at 5 to 20 ° C before and after the complete color development point, and the mutual shade change is over. By wrapping, the gradation effect of light transmission can be obtained in a wide temperature range. Therefore, the dimming sheet of the present invention does not define only those having a narrow discoloration temperature range and sharp discoloration. Further, although four or more types of microcapsules having color development points in different temperature zones can be used in combination, the gradation change of the light transmittance may not be much different from that in the case of using three types in combination. The total amount of the decolorizing / coloring reversible microcapsules is 0.5 to 20% by mass, particularly 1 to 10% by mass, based on the thermosetting resin layer.

The flexible dimming sheet of the present invention preferably contains a cloth in the core material for the purpose of dimensional stability of the dimming sheet, prevention of tear breakage, etc., and its specifications include "surface protective layer / cloth / temperature-sensitive discoloration". "Resin layer / back surface resin layer", "front surface protective layer / thermochromic resin layer / fabric / back surface resin layer", and "front surface protective layer / thermochromic resin layer / fabric / thermochromic resin layer / back surface" It can be designed as a "resin layer". The fabric does not impede light transmission, for example, the fabric itself is semi-transmissive and has a total light transmission rate (JIS K7375: 2008) of 50 to 85%. If the fabric has a void ratio of 1 to 10%, the fabric has a void ratio of 10 to 35% having many voids in the weave, or a coarse woven fabric having a large void ratio of 35 to 95% in a gap having a particularly wide thread spacing. , Woven fabric, knitted fabric, or non-woven fabric. The woven fabrics are warp and weft groups, and plain woven fabrics and basket woven fabrics (for example, regular basket woven fabrics such as 2x2, 3x3, 4x4, 3x2, 4x2, etc. Irregular basket weaves such as 4x3, 2x3, 2x4, 3x4), twill fabrics (3 diagonals, 4 diagonals, 5 diagonals, etc.), Akiko fabrics (2 jumps, 3) Regular woven fabrics such as jumps and 4 jumps), and these modified woven fabrics, as well as torn diagonal woven fabrics, mojiri woven fabrics (gauze woven fabrics, woven fabrics), Russell knitted fabrics, lace knitted fabrics, etc. Basket woven fabric is preferable because it has an excellent balance of warp and weft properties. Further, it includes a warp yarn group, an upper right bias yarn group and an upper left bias yarn group, and is a triaxial plain woven fabric, a triaxial basket woven fabric (for example, 2 × 2, 3 × 3) and the like by these yarn groups. There is no limitation on the driving density of the warp and weft, or the warp and bias yarn of the cloth (woven fabric), and an arbitrary driving density can be designed according to the thickness (denier) of the yarn used. These fabrics (woven fabrics) may be subjected to one or more known fiber treatments such as scouring, water repellent treatment, silane coupling agent treatment, organic titanate treatment, binder resin fixing, and adhesive coating. ..

Multifilament yarns, short fiber spun yarns, and monofilament yarns can be used as the warp yarns and weft yarns forming the above-mentioned fabric, and in particular, the number of filaments is 30 to 300, the fineness is 138 to 2223dtex, and preferably 277 to 1112dtex. It is a multifilament thread. The types of fibers are natural fibers such as Kenaf and cotton (used as short fiber spun yarn), polypropylene, polyethylene, polyester (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc.), nylon, vinylon, acrylic, aromatic. Polyester-based, aromatic polyamide-based, aromatic heterocyclic polymer (polyimidazole-based, polyoxazole-based, etc.) synthetic fiber group, glass, silica, basalt, alumina, boron, carbon, stainless steel and other inorganic fiber groups, and these Examples include mixed fibers and core-sheath fibers. In particular, the resistance to tear fracture of the light control sheet body obtained by using fibrous threads made of an aromatic polyester type, an aromatic polyamide type, an aromatic heterocyclic polymer type, etc. is enhanced. Further, fire resistance and nonflammability can be imparted to the light control sheet obtained by using inorganic fiber threads made of glass, silica, basalt, alumina, carbon or the like. In addition, the fiber woven fabric has a water-repellent treatment to prevent water from entering from the cross section of the multifilament thread due to the capillary phenomenon, a flame-proof treatment to impart self-extinguishing property at the time of ignition, or a coating resin layer. Adhesive treatment can be applied to improve the adhesion with.

It is preferable to provide an antifouling layer on the surface protective layer of the flexible light control sheet of the present invention, and examples of the antifouling layer include acrylic resin, fluorine-based copolymer resin, acrylic-silicon copolymer resin, and acrylic. Fluorine copolymer resin, acrylic-urethane copolymer resin, blend of acrylic resin and fluorine copolymer resin, and silica fine particles, colloidal silica, organosilicate, silane coupling agent, ultraviolet absorber (paragraph [paragraph] 0016] is the outermost layer containing the above. Examples of the formation of these antifouling layers are formed by applying and drying a resin solution soluble in a solvent or an emulsion liquid 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, by further providing a photocatalytic layer containing a photocatalytic inorganic material (for example, photocatalytic titanium oxide, photocatalytic tungsten oxide, etc.) on these antifouling layers, it is possible to prevent rain streaks (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, high molecular weight heterocyclic polymer, conductive metal nanoparticles, etc.) in order to suppress the adhesion of dust. Can be done.

The flexible dimming sheet (1) of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 includes a cloth (2) as a base cloth, one side of which is covered with a thermosetting resin layer (3), and a surface protective layer (4) is further coated on (3) to form (2). It is a figure which shows an example of the cross section of the flexible light control sheet (1) which coated the back surface with the back surface resin layer (5), and FIG. 2 shows the cloth (2) as a base cloth, and one side thereof is a surface protection layer. A flexible dimming sheet (1) coated with (4), the back surface of (2) coated with a thermosetting resin layer (3), and further coated with a back surface resin layer (5) on top of (3). It is a figure which shows an example of the cross section of).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, the dimming effect of the test sheet was measured and evaluated by the following test method.
1) Dimming effect While raising the temperature of a 10 cm x 10 cm square sheet piece from 20 to 80 ° C at a rate of 1 ° C / min, the total light transmittance (JIS K7375: 2008) is continuously measured by an integrating sphere color measuring device. The measurement was performed to determine the change point (decolorization point) of the total light transmittance.
2) Dimming effect after weather resistance test Outdoor exposure test (Soka City, Saitama Prefecture: Expanded to a southward inclination of 35 ° from May) 10 cm x 10 cm square from the expanded sheet 3 months, 6 months, and 1 year later The sheet piece of No. 1 was collected, and the change point (decolorization point) of the total light transmittance was determined in the same manner as in the above method.

[Example 1]
As the cloth, a polyester multifilament plain woven fabric: (277dtex × 277dtex) / (12 pieces / 25.4 mm × 13 pieces / 25.4 mm), a mass of 65 g / m ² , and a porosity of 31% were used.
Surface protection layer The soft vinyl chloride resin compound composition of Formulation 1 below was placed in a calendar molding machine with a roll temperature of 180 to 190 ° C., and had 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-polymerized polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamole DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate ester (flameproofing agent) 10 parts by mass Zinc oxide (white fine particles) ) 10 parts by mass Benzotriazole compound (ultraviolet absorber) 0.2 parts by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass
Backside resin layer The soft vinyl chloride resin compound composition of Formulation 2 below was placed in a calendar molding machine with a roll temperature of 180 to 190 ° C., and had a thickness of 0.12 mm and a total light transmittance (JIS K7375) of 77%. The film was used as the back surface resin layer.
[Formulation 2] Soft vinyl chloride resin compound composition Suspension-polymerized polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Product name: Hexamole DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate (flameproofing agent) 10 parts by mass Antimon trioxide (flame retardant) Auxiliary agent) 1 part by mass Benzotriazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.2 parts by mass
Thermosetting Discoloration Resin Layer The soft vinyl chloride resin compound composition of Formulation 3 below was applied to a calendar molding machine with a roll temperature of 180 to 190 ° C., and the thickness was 0.15 mm and the total light transmittance (JIS K7375) was 64%. The semi-transmissive film was used as a thermosetting resin layer.
[Formulation 3] Soft vinyl chloride resin compound composition Suspension-polymerized 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 mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate (flameproofing agent) 10 parts by mass Antimon trioxide (flame retardant) Auxiliary agent) 1 part by mass Benzotriazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass
Reversible decolorization / color development microcapsules (1) 10 parts by mass * 3- [2-ethoxy-4- (N-ethylanilino)]-3- (1-ethyl-2-methylindole-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 color development temperature: 42 ° C: colorless → Light blue → blue)
Dimming sheet (1)
Using a laminator with a roll setting of 180 ° C., a laminated sheet (1) having a thickness of 0.72 mm having a “surface protective layer / thermosetting resin layer / fabric / back surface resin layer” was obtained. The transmitted 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 → pale blue → blue was completed, and the change was completed. A reversible dimming function that limits the total light transmittance to 13% , gradually returns to colorless at temperatures below 42 ° C, and the sheet becomes colorless again near room temperature, and the total light transmittance gradually expands to 25%. Was expressed, and the same reversible dimming function was maintained even one year after outdoor exposure.

[Example 2]
Except for changing the decolorization / color reversible microcapsules (1) 10 parts by mass of the thermosetting resin layer (formulation 3) of Example 1 to the decolorization / color reversible microcapsules (2) 10 parts by mass. Obtained a laminated sheet (2) having a thickness of 0.72 mm in the same manner as in Example 1. The transmitted 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 → pale red → red was completed, and the change was completed. The total light transmittance is limited to 10% , gradually returns to colorless at temperatures below 52 ° C, and the sheet becomes colorless again near room temperature, and the total light transmittance is gradually expanded to 26%. It developed a function and maintained the same reversible dimming function even one year after outdoor exposure.
* Reversible microcapsules for decolorization / color development (2)
9-Ethyl (3-methylbutyl) amino-spiro [12H-benzoxanthene-12,1'(3'H) isobenzofuran] -3'-one 5% by mass and dodecyl gallate / stearyl gallate 25% by mass Microcapsules of melamine resin shell wall (45% by mass) containing 25% by mass of heptyl stearate / docosan / lauryl alcohol (complete color development temperature: 52 ° C: colorless → pale red → red)

[Example 3]
Except for changing 10 parts by mass of the reversible microcapsules of decolorization / color development of the thermosetting resin layer (formulation 3) of Example 1 to 10 parts by mass of the reversible microcapsules of decolorization / color development (3). Obtained a laminated sheet (3) having a thickness of 0.72 mm in the same manner as in Example 1. The transmitted color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 27%, but the change of colorless → light orange → orange was completed at a temperature of 62 ° C or higher. , Its total light transmittance is limited to 12% , gradually returns to colorless at temperatures below 62 ° C, and the sheet becomes colorless again near room temperature, and the total light transmittance gradually expands to 27%. It developed a light function and maintained the same reversible dimming function even one year after outdoor exposure.
* Reversible microcapsules for decolorization / color development (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. Color development temperature: 62 ° C: colorless → light orange → orange)

[Example 4]
A laminated sheet (4) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the thermosetting resin layer (formulation 3) of Example 1 was changed to the following formulation 4. The transmitted 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 → pale blue → blue was completed, and the change was completed. The total light transmittance is limited to 16%, and the change from bluish purple to purple (blue of microcapsules (1) + red of microcapsules (2)) is completed at a temperature of 52 ° C or higher, and the temperature of the sheet rises. As a result, the total light transmittance is gradedly limited from 26% to 10%, and then as the temperature of the sheet drops, the sheet turns bluish purple → blue again at a temperature around 42 ° C and all light rays. Gradation reversible dimming function in which the transmittance is gradually expanded to 16%, and the sheet becomes blue → pale blue → colorless again at around room temperature, and the total light transmittance is gradually expanded to 26%. Was expressed, and the same reversible dimming function was maintained even one year after outdoor exposure.
[Formulation 4] Soft vinyl chloride resin compound composition Suspension-polymerized 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 mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate (flameproofing agent) 10 parts by mass Antimon trioxide (flame retardant) Auxiliary agent) 1 part by mass Benzotriazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass
Reversible decolorization / color development microcapsules (1) 5 parts by mass
Decolorization / color reversible microcapsules (2) 5 parts by mass

[Example 5]
A laminated sheet (5) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the thermosetting resin layer (formulation 3) of Example 1 was changed to the following formulation 5. The transmitted color of the obtained sheet was colorless at room temperature, and its total light transmittance (JIS K7375) was 25%, but the change of colorless → pale red → red was completed at a temperature of 52 ° C or higher, and the change was completed. The total light transmittance is limited to 15%, and the change from red to dark orange (red of microcapsules (2) + orange of microcapsules (3)) is completed at a temperature of 62 ° C or higher, and the temperature of the sheet. As the temperature of the sheet rises, the total light transmittance is gradually limited from 25% to 7%, and then as the temperature of the sheet drops, 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 becomes red → pale red → colorless again at around room temperature, and the total light transmittance is gradually expanded to 25%. It developed a dimming function and maintained the same reversible dimming function even one year after outdoor exposure.
[Formulation 5] Soft vinyl chloride resin compound composition Suspension-polymerized polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Trade name: Hexamole DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate (flameproofing agent) 10 parts by mass Antimon trioxide (flame retardant) Auxiliary agent) 1 part by mass Benzotriazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass
Decolorization / color reversible microcapsules (2) 5 parts by mass
Decolorization / color reversible microcapsules (3) 5 parts by mass

[Example 6]
A laminated sheet (6) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that the thermosetting resin layer (formulation 3) of Example 1 was changed to the following formulation 6. The transmitted 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 → pale blue → blue was completed, and the change was completed. The total light transmittance is limited to 18%, and the change of blue → bluish purple → purple (blue of microcapsules (1) + red of microcapsules (2)) is completed at a temperature of 52 ° C or higher, and the total light transmittance is completed. The rate is limited to 11%, and the change from purple to dark purple (blue of microcapsules (1) + red of microcapsules (2) + orange of microcapsules (3)) is completed at a temperature of 62 ° C or higher. As the temperature of the sheet rises, its total light transmittance is gradationally limited from 24% to 6%, and then as the temperature of the sheet drops, the sheet becomes dark purple again at a temperature around 52 ° C. → Purple and total light transmittance gradually expanded to 11%, and at a temperature of 42 ° C or less, the sheet again became purple → bluish purple → blue and the total light transmittance gradually expanded to 18%. Furthermore, at around room temperature, the sheet turns blue → pale blue → colorless again, and the total light transmittance gradually expands to 24%, exhibiting a gradation reversible dimming function, which is equivalent even one year after outdoor exposure. It retained a reversible dimming function.
[Formulation 6] Soft vinyl chloride resin compound composition Suspension-polymerized 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 mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate (flameproofing agent) 10 parts by mass Antimon trioxide (flame retardant) Auxiliary agent) 1 part by mass Benzotriazole compound (ultraviolet absorber) 0.2 part by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass
Reversible microcapsules for decolorization / color development (1) 3 parts by mass
Reversible microcapsules for decolorization / color development (2) 4 parts by mass
Decolorization / color reversible microcapsules (3) 3 parts by mass

[Example 7]
The "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" configuration of Example 1 is changed to the "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" configuration of Example 1. A laminated sheet (7) having the same performance as that of the above was obtained.

[Example 8]
The configuration of "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" of Example 2 is changed to the configuration of "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" of Example 2. A laminated sheet (8) having the same performance as that of the above was obtained.

[Example 9]
The "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" configuration of Example 3 is changed to the "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" configuration of Example 3. A laminated sheet (9) having the same performance as that of the above was obtained.

[Example 10]
The "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" configuration of Example 4 is changed to the "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" configuration of Example 4. A laminated sheet (10) having the same performance as that of the above was obtained.

[Example 11]
Example 5 has the "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" configuration as the "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" configuration. A laminated sheet 11) having the same performance as the above was obtained.

[Example 12]
The "front surface protective layer / thermosetting resin layer / fabric / back surface resin layer" configuration of Example 6 is changed to the "front surface protective layer / fabric / thermosetting resin layer / back surface resin layer" configuration of Example 6. A laminated sheet (12) having the same performance as that of the above was obtained.

[Examples 13 to 24]
An antifouling layer according to 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 in Examples 1 to 12, and further, an antifouling layer. Laminated sheets (13) to (24) attached to the above were obtained.
<Anti-fouling layer>
The dimming sheet of Examples 1 to 12 was applied to a coating machine under 80 mesh gravure roll coating conditions, and the surface protective layer was coated with the antifouling composition of [Formulation 7], and in a hot air furnace at 120 ° C. It was dried for 3 minutes to provide an antifouling layer.
[Formulation 7] Antifouling layer composition Silica sol (particle size 20 to 30 nm: solid content 48% by mass) 100 parts by mass Vinyl triethoxysilane (silane coupling agent) 50 parts by mass Cerium oxide particles (particle size 15 nm: ultraviolet absorber) ) 5 parts by mass Polyethylene glycol type non-ionic activator (antistatic agent) 1 part by mass Diluting agent (water) 200 parts by mass

[Comparative Example 1]
A laminated sheet having a thickness of 0.6 mm and having a "thermosetting resin layer / fabric / back surface resin layer" configuration in the same manner 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 laminated sheet (25) exhibited the same dimming function as the dimming sheet of Example 1, but was decolorized / developed after 3 months of outdoor exposure from May to July. The reversible microcapsules (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light transmitting color of the laminated sheet (25) no longer changed, and the dimming function was lost.

[Comparative Example 2]
A laminated sheet having a thickness of 0.6 mm and having a "thermosetting resin layer / fabric / back surface resin layer" configuration in the same manner as in Example 2 except that the surface protective layer is omitted from the light control sheet of Example 2. (26) was obtained. The obtained laminated sheet (26) exhibited the same dimming function as the dimming sheet of Example 2, but was decolorized / developed after 3 months of outdoor exposure from May to July. The reversible microcapsules (2) deteriorated and the red color exhibited at a temperature of 52 ° C. or higher became colorless, and the light transmitting color of the laminated sheet (26) no longer changed, and the dimming function was lost.

[Comparative Example 3]
A laminated sheet having a thickness of 0.6 mm and having a "thermosetting resin layer / fabric / back surface resin layer" configuration in the same manner 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 laminated sheet (27) exhibited the same dimming function as the dimming sheet of Example 3, but was decolorized / colored after 3 months of outdoor exposure from May to July. The reversible microcapsules (3) deteriorated and the orange color exhibited at a temperature of 62 ° C. or higher became colorless, and the light transmitting color of the laminated sheet (27) no longer changed, and the dimming function 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 laminated 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 laminated sheet (28) exhibited the same dimming function as the dimming sheet of Example 1, but was decolorized / colored 6 months after outdoor exposure from May to October. The reversible microcapsules (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light transmitting color of the laminated sheet (28) no longer changed, and the dimming function was lost.

[Comparative Example 5]
In the light control sheet of Example 1, 0.2 parts by mass of a benzotriazole compound (ultraviolet absorber) and cerium oxide (ultraviolet absorber) from the soft vinyl chloride resin compound composition of the surface protective layer (formulation 1). A laminated 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 was omitted and a light transmissive film having a total light transmittance of 66% was used as the surface protective layer. The obtained laminated sheet (29) exhibited the same dimming function as the dimming sheet of Example 1, but was decolorized / colored 6 months after outdoor exposure from May to October. The reversible microcapsules (1) deteriorated and the blue color exhibited at a temperature of 42 ° C. or higher became colorless, and the light transmitting color of the laminated sheet (29) no longer changed, and the dimming function 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 a silicone elastomer) according to the following formulation 8, and the thickness was 0.12 mm, and the total light transmittance (JIS K7375). A laminated sheet (30) having a thickness of 0.72 mm was obtained in the same manner as in Example 1 except that a 71% light transmissive film was used. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (1), and had the same reversible dimming function even one year after outdoor exposure.
[Formulation 8] Soft vinyl chloride resin compound composition Suspension-polymerized polyvinyl chloride resin (degree of polymerization 1300) 100 parts by mass 1,2-cyclohexanedicarboxylic acid diisononyl ester 50 parts by mass * Trade name: Hexamole DINCH (manufactured by BASF)
Epoxidized soybean oil (plasticizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Aromatic phosphate ester (flameproofing agent) 10 parts by mass Silicon elastomer 10 parts by mass Benzo Triazole compound (ultraviolet absorber) 0.2 parts by mass * 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-)
Phenylethyl) Phenol Cerium oxide (ultraviolet absorber) 0.4 parts by mass

[Example 26]
A laminated 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 of Example 2 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (2), and had the same reversible dimming function even one year after outdoor exposure.

[Example 27]
A laminated 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 of Example 3 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (3), and had the same reversible dimming function even one year after outdoor exposure.

[Example 28]
A laminated 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 of Example 4 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (4), and had the same reversible dimming function even one year after outdoor exposure.

[Example 29]
A laminated 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 of Example 5 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (5), and had the same reversible dimming function even one year after outdoor exposure.

[Example 30]
A laminated 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 of Example 6 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (6), and had the same reversible dimming function even one year after outdoor exposure.

[Example 31]
A laminated 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 of Example 7 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (7), and had the same reversible dimming function even one year after outdoor exposure.

[Example 32]
A laminated 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 of Example 8 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (8), and had the same reversible dimming function even one year after outdoor exposure.

[Example 33]
A laminated 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 of Example 9 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet was equivalent to that of the laminated sheet (9), and had the same reversible dimming function even one year after outdoor exposure.

[Example 34]
A laminated 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 of Example 10 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (10), and had the same reversible dimming function even one year after outdoor exposure.

[Example 35]
A laminated 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 of Example 11 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (11), and had the same reversible dimming function even one year after outdoor exposure.

[Example 36]
A laminated 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 of Example 12 was replaced with the surface protective layer of Example 25. The dimming function of the obtained sheet had the same performance as that of the laminated sheet (12), and had the same reversible dimming function even one year after 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 further attached with the same performance as in Examples 25 to 36. Laminated sheets (42) to (53) were obtained.

In the flexible daylighting sheet of the present invention, the light transmission of the sheet is controlled in a gradation by a change in temperature, and particularly when the surface temperature of the sheet reaches 30 ° C to 70 ° C during the daytime, the light transmission of the sheet body is transmitted. The rate is gradually attenuated to create a blackout curtain effect, which keeps the internal temperature low by about 1 ° C to 5 ° C, and in the evening when the temperature drops, the light transmission rate is gradually increased indoors. The effect of ensuring daylighting is repeatable in response to changes in temperature, and because it has excellent weather resistance and flexibility, daylighting / blind windows for large membrane structure facilities such as sports stadiums and daylighting / blind windows for seat warehouses. It is suitable for use in industrial materials such as daylighting / blind windows for truck hoods, building curing sheets, ceiling film materials, space partition sheets, daylighting / blind windows for sheet shutters, store eaves tents, and veranda awning sheets. ..

1: Flexible light control sheet 2: Fabric 3: Thermosetting resin layer 4: Front surface protective layer 5: Back surface resin layer

Claims (3)

A light-transmitting laminate including a front surface protective layer and a back surface resin layer, and a temperature-sensitive discoloration resin layer in the middle, at least the surface protective layer is semi-transmissive and UV-shielding. 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 discoloration resin layer contains reversible microcapsules for decolorization / color development. , This reversible microcapsule has a perfect color development point in any of the temperature zones of 30 to 46 ° C., 47 to 55 ° C., and 56 ° C. or higher, and the temperature of the light transmissive laminate becomes the perfect color development point. When it reaches, the color of the thermochromic resin layer reduces the total light transmittance (JIS K7375: 2008) of the light-transmitting laminate, and the temperature of the light-transmitting laminate is completely colored. A flexible dimming sheet characterized in that when the temperature drops below a point, the total light transmittance of the light-transmitting laminate is increased by decolorizing the temperature-sensitive discoloration resin layer. Claim that the temperature-sensitive discoloration resin layer contains two or three types of decolorizing / coloring reversible microcapsules, and the difference in complete color development points of the individual decolorizing / coloring reversible microcapsules is 5 ° C. or more. The flexible dimming sheet according to 1. The light-transmitting laminate contains a cloth, and includes "front surface protective layer / cloth / thermosetting resin layer / back surface resin layer", "front surface protective layer / thermosetting resin layer / cloth / back surface resin layer", and The flexible dimming according to claim 1 or 2, which is any one of the configurations selected from "front surface protective layer / thermosetting resin layer / fabric / thermosetting resin layer / back surface resin layer". Sheet.