High light-transmitting insect-repellent and heat-shielding sheet

Abstract

This highly transparent, insect-repellent, heat-shielding sheet offers both transparency and heat-shielding and insect-repellent properties, providing stable and sustainable insect-repellent effects against flying insects such as moths, flies, and mosquitoes in extremely hot environments where heat shielding is required. It is suitable for use in retractable sheet shutters, partitions, and other applications. [Solution] A laminated sheet comprising a grid-like substrate, which is a woven fabric or a net, with a heat-shielding layer provided on at least one surface, wherein the heat-shielding layer contains at least luminous mica particles and a pyrethroid compound / cellulose nanofiber composite, and the pyrethroid compound / cellulose nanofiber composite contains cellulose nanofibers that have adsorbed a portion of the pyrethroid compound.

Description

Technical Field

[0001] The present invention relates to a heat-insulating and highly light-transmissive partition sheet having pest-repellent properties, which is used for lift-up seat shutters at factory and in-factory warehouse entrances and exits, tent structures in outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, etc.), open terrace shelters and parasols, horticultural and orchard sunshade enclosures, partitions in factories and research facilities, partitions in hospitals and medical facilities, partition stalls, and the like.

Background Art

[0002] As general-purpose flexible partition sheets, there are laminated bodies with a thickness of 0.25 mm to 0.50 mm (film part within the grid) obtained by thermally laminating a transparent soft vinyl chloride resin film on both sides of a lattice-shaped net or a mesh-shaped fabric as a base material, and also noren-style curtains with a thickness of 0.50 mm to 2.0 mm without a base material. These flexible partition sheets are widely used in various applications such as lift-up seat shutters at factory and in-factory warehouse entrances and exits, tent structures in outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, etc.), pool fences, open terrace shelters and parasols, horticultural and orchard sunshade enclosures, partitions in factories and research facilities, partitions in hospitals and medical facilities, partition stalls, and the like.

[0003] In particular, partition sheet materials such as automatic lifting sheet shutters and curtain-type screens installed at the entrances and exits of factories and factory warehouses are commonly colored yellow to orange to prevent phototactic insects such as moths, flies, midges, and stink bugs from entering the factory. Phototactic insects sense wavelengths of 250-650 nm and also sense ultraviolet light in the 250-380 nm range, which is invisible to humans, and are particularly attracted to ultraviolet light emitted from lighting lamps, leading to problems with their entry. This insect-repellent coloring absorbs and cuts wavelengths of 400-480 nm, and by using ultraviolet absorbers in combination, it also absorbs and cuts wavelengths below 380 nm, thereby dulling the light-sensing ability of phototactic insects. Inventions of partition sheets such as those disclosed in Patent Documents 1 and 2 have been disclosed. However, with the global shift to LED lighting in the lighting market, ultraviolet and thermal radiation from lamps has been almost eliminated, reducing the attraction of phototactic insects to light sources. Nevertheless, for wavelengths between 400 and 650 nm, the blinding effect (decreased light perception) of yellow light remains. On the other hand, nocturnal moths, which exhibit negative phototaxis, are at high risk of being preyed upon by birds during the day, so they have a habit of becoming immobile at night, mistaking the light for daylight, in order to avoid predation. Yellow light around 570 nm, in particular, easily triggers a photoreaction (daylight illusion) in the compound eyes, and yellow light moth repellent lamps are used in agricultural fields as a means of preventing the attraction of nocturnal moths.

[0004] On the other hand, there are various problems caused by pests that are not related to phototaxis, such as cockroaches and flies that are attracted to odorous substances emitted from fresh food, fermented products, and food waste for the purpose of feeding and laying eggs, as well as blood-sucking insects such as mosquitoes and gnats that are attracted to odorous substances contained in the breath and sweat of humans and animals. Sheet shutters colored in yellow to orange and curtains have not shown any significant effect in preventing the entry of these pests. Meanwhile, for household use, products using evaporative pyrethroid insecticides with insecticidal and paralyzing (knockdown) effects are commercially available as insect repellent (repellent) means mainly targeting flies, mosquitoes, cockroaches, and mites (such as insect repellent sheets for wardrobes and insecticide aerosols). This pyrethroid insecticide has been applied to partition materials such as those described in Patent Documents 1 and 2, resulting in the invention of partition sheets (Patent Document 3), which makes it possible to obtain insecticidal effects against both pests related to phototaxis and pests unrelated to phototaxis. However, with sheet shutters and curtain-type screens colored yellow to orange, sunlight entering the factory or facility causes the area near the entrance to be illuminated with a yellow to orange translucent color, creating an unusual indoor environment. Furthermore, at night, the yellow to orange translucent light leaking from indoors becomes conspicuous, leading to a recent decline in new demand.

[0005] On the other hand, in summer when extremely hot days become commonplace, heat-shielding properties are required for partition sheet materials such as sheet shutters and curtain-type curtains, and it is desirable to suppress the temperature rise near the entrance by several degrees when they are closed for long periods of time. However, if insect repellent properties are also applied, there is a problem that evaporative pyrethroid insecticides will not last through the summer due to the extreme heat. The applicant disclosed a technology using cyclodextrin supported with a pyrethroid compound in an invention of an industrial material sheet that provides long-term stable control (repellent) effects against flying insects (Patent Document 4). While this industrial material sheet does indeed provide long-term stable control (repellent) effects against flying insects, the use of cyclodextrin causes the sheet to become cloudy, hindering visibility to the other side of the sheet, thus limiting its application to partition sheet materials such as sheet shutters and curtain-type curtains. Furthermore, the applicant has proposed an invention (Patent Document 5) that contains interference mica particles and ultrafine titanium dioxide and / or ultrafine zinc oxide as a highly translucent film material that has harmful ultraviolet and infrared shielding properties and excellent light transmission properties. Applying pyrethroid insecticides to this highly translucent film material makes it possible to simply combine heat shielding and insecticidal effects, but it has remained difficult to stably maintain the retention of evaporative pyrethroid insecticides in extremely hot environments. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 62-278931 [Patent Document 2] Japanese Patent Publication No. 2002-114606 [Patent Document 3] Japanese Patent Publication No. 2020-109070 [Patent Document 4] Japanese Patent Publication No. 2014-223044 [Patent Document 5] Japanese Patent Publication No. 2010-099959 [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention aims to provide a highly transparent, insect-repellent, heat-shielding sheet that combines transparency (visibility to the other side of the sheet) with heat-shielding and insect-repellent properties, and that provides stable and sustainable insect-repellent effects against flying insects such as moths, flies, and mosquitoes in extremely hot environments where heat shielding is required. If this problem can be solved, the insect-repellent effect will be sustained in extremely hot environments, enabling a wide range of applications such as retractable sheet shutters at factory and warehouse entrances, tent structures for outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, etc.), open terrace awnings and parasols, sunshade enclosures for gardens and orchards, partitions inside factories and research facilities, partitions inside hospitals and medical facilities, and partitioned stalls. Furthermore, by extending the product lifecycle, the waste of resources required for manufacturing partition sheets will be reduced, contributing to the reduction of greenhouse gas emissions. [Means for solving the problem]

[0008] As a result of considering these points and conducting extensive research, the present invention has been completed. The present invention is a laminated sheet comprising a heat-shielding layer provided on at least one surface of a grid-like substrate, such as a woven fabric or a net, wherein the heat-shielding layer contains at least luminous mica particles and a pyrethroid compound / cellulose nanofiber composite, and the pyrethroid compound / cellulose nanofiber composite contains cellulose nanofibers that adsorb a portion of the pyrethroid compound, thereby providing transparency (visibility to the other side of the sheet), combining heat-shielding and insect-repellent effects, and enabling the provision of a highly transparent insect-repellent and heat-shielding sheet that provides stable and sustainable insect-repellent effects against flying insects such as moths, flies, and mosquitoes in extremely hot environments. In particular, it is preferable that the cellulose nanofibers adsorb and support a portion of the total amount of the pyrethroid compound. By adsorbing (impregnating) pyrethroid compounds (liquid) onto cellulose nanofibers, the transparency of the cellulose nanofibers is increased (by creating a wet state to suppress diffuse reflection and synchronize the refractive index). At the same time, while ensuring the transparency of the highly translucent insect-repellent and heat-shielding sheet, excessive transpiration of pyrethroid compounds in extremely hot environments is controlled, thereby enabling long-term sustained release stability.

[0009] The highly translucent insect-repellent heat-shielding sheet of the present invention is composed of luminous mica particles made of synthetic mica and a thin film coating layer, wherein the thin film coating layer is preferably one of the following: a single layer of titanium dioxide, two layers of titanium dioxide / silicon dioxide, and three layers of titanium dioxide / silicon dioxide / titanium dioxide. The coating layer of luminous mica particles refracts and reflects near-infrared rays, thereby exhibiting a heat-shielding effect. This heat-shielding effect suppresses heat accumulation and temperature rise in the highly translucent insect-repellent heat-shielding sheet itself. This suppression effect controls the excessive evaporation of pyrethroid compounds (insecticides), enabling long-term, stable sustained release.

[0010] The highly light-transmitting insect-repellent and heat-shielding sheet of the present invention comprises the pyrethroid compounds empenthrin, flamethrin, prallethrin, allethrin, imiprothrin, pyrethrin, phthalthrin, resmethrin, phenothrin, metofluthrin, synerin II, transfluthrin, jasmolin II, cyphenothrin, peratrin, etofenprox, monfluorothrin, permethrin, It is preferable that the pyrethroid compounds are silafluofen, tefluthrin, bifenthrin, and cyfluthrin. By incorporating such pyrethroid compounds at a concentration of 1 to 5% by mass relative to the mass of the heat shielding layer, an insecticidal effect (insecticide, repellent, or knockdown) is obtained mainly against flying insects such as moths, flies, and mosquitoes. In particular, it is preferable that two pyrethroid compounds are used in combination, with a molecular weight difference between the two being 40 to 160, and the mass ratio of the pyrethroid compound with the smaller molecular weight to the pyrethroid compound with the larger molecular weight being 1:3 to 3:1. By setting the molecular weight difference to 40 to 160 and further specifying the ratio of their combination, a time-delay effect ranging from rapid action (fast-acting) to residual action (long-lasting effect) is provided for insecticidal effects (insecticide, repellent, or knockdown) depending on the type of insect such as moths, flies, and mosquitoes, making long-term effectiveness efficient.

[0011] The highly light-transmitting insect-repellent heat-shielding sheet of the present invention preferably contains an ultraviolet-excited keto / enol type tautomer in its heat-shielding layer, wherein the ultraviolet-excited keto / enol type tautomer is one or more selected from benzotriazole compounds, triazine compounds, and diphenyl ketone compounds. The ultraviolet-excited keto / enol type tautomer generates molecular motion by reversibly repeating tautomerism between keto and enol types upon ultraviolet excitation, and exhibits the effect of converting ultraviolet energy into thermal energy and releasing it, that is, mitigating the effects of ultraviolet light. This detoxification of ultraviolet light prevents ultraviolet degradation of the highly light-transmitting insect-repellent heat-shielding sheet and pyrethroid compounds, and at the same time cuts wavelengths below 380 nm that insects sense, thus contributing to suppressing the attraction of phototactic insects indoors.

[0012] The highly light-transmitting insect-repellent heat-shielding sheet of the present invention preferably has a heat-shielding layer that contains one or more near-infrared absorbing materials selected from tungsten oxide, indium oxide, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO), aluminum-doped zinc oxide (AZO), lanthanum hexaboride (LaB6), phthalocyanine compounds, naphtholquinone compounds, iminium compounds, anthraquinone compounds, aminium compounds, and nickel-thiol complex compounds, and the heat-shielding layer is preferably colored. These near-infrared absorbing materials have high visible light transmittance and excellent solar radiation shielding function, and exhibit a heat-shielding effect through synergy with the near-infrared refraction and reflection of luminous mica particles within the same layer. This heat-shielding effect suppresses heat accumulation and temperature rise in the highly translucent insect-repellent heat-shielding sheet itself, controlling the excessive evaporation of pyrethroid compounds (insecticides) and ensuring a stable, long-term sustained release effect.

[0013] The highly translucent insect-repellent heat-shielding sheet of the present invention has an antifouling layer provided on top of the heat-reflective layer, and preferably contains one or more near-infrared absorbing materials selected from tungsten oxide, indium oxide, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO), aluminum-doped zinc oxide (AZO), and lanthanum hexaboride (LaB6) within this antifouling layer, and the antifouling layer preferably possesses both antifouling and heat-shielding properties. These near-infrared absorbing materials have high visible light transmittance and excellent solar radiation shielding function, and exhibit a heat-shielding effect through synergy with the near-infrared refraction and reflection of the luminous mica particles in the heat-reflective layer and other layers. This heat-shielding effect suppresses heat accumulation and temperature rise of the highly translucent insect-repellent heat-shielding sheet itself. This suppression effect controls the excessive evaporation of pyrethroid compounds (insecticides), enabling further sustained and stable release. [Effects of the Invention]

[0014] This invention provides a highly translucent, insect-repellent, heat-shielding sheet that is transparent (allows visibility to the other side of the sheet) and combines heat-shielding and insect-repellent properties. It enables the provision of a highly translucent, insect-repellent, heat-shielding sheet that provides stable and sustainable insect-repellent effects against flying insects such as moths, flies, and mosquitoes in extremely hot environments where heat shielding is required. By providing this highly translucent, insect-repellent, heat-shielding sheet, the insect-repellent effect in extremely hot environments is sustained, enabling a wide range of applications such as retractable sheet shutters at factory and warehouse entrances, outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, tent structures, etc.), pool fences, open terrace awnings and parasols, sunshade enclosures for gardens and orchards, partitions in factories and research facilities, partitions in hospitals and medical facilities, and partitioned stalls. Furthermore, by extending the product lifecycle, the waste of resources required for manufacturing partition sheets is reduced, contributing to the reduction of greenhouse gas emissions. [Modes for carrying out the invention]

[0015] The present invention provides a highly light-transmitting insect-repellent and heat-shielding sheet, a laminated sheet comprising a heat-shielding layer on at least one surface of a grid-like substrate which is a woven fabric or net, wherein the heat-shielding layer contains at least luminous mica particles and a pyrethroid compound / cellulose nanofiber composite, the pyrethroid compound / cellulose nanofiber composite comprises cellulose nanofibers on which a portion of the pyrethroid compound has been adsorbed, and further comprising synthetic mica and a thin film coating layer, the thin film coating layer being a single layer of "titanium dioxide" and "titanium dioxide / The heat shielding layer is configured to be one of two layers of silicon dioxide or three layers of titanium dioxide / silicon dioxide / titanium dioxide, and further comprises an ultraviolet-excited keto / enol type tautomer (one or more selected from benzotriazole compounds, triazine compounds, and diphenyl ketone compounds), further comprises a near-infrared absorbing material and is colored, and further comprises an antifouling layer provided on top of the heat reflective layer, with a near-infrared absorbing material contained within the antifouling layer, so that the antifouling layer has both antifouling and heat shielding properties.

[0016] The woven fabric used as the grid-like base material for the highly light-transmitting insect-repellent and heat-shielding sheet of the present invention may be: 1) a square grid-like open-mesh fabric plain woven or gauze woven with warp / multifilament yarns and weft / multifilament yarns; or 2) a triangular grid-like triaxial open-mesh fabric plain woven or gauze woven with warp / multifilament yarns, particularly with 30° left-upward bias and 30° right-upward bias / multifilament yarns; or 3) warp and weft / multifilament yarns Selected from, in particular, tetraaxial fabrics including square / triangular grid openings woven in plain weave or gauze with warp and weft / multifilament yarn groups with a 45° left-upward and 45° right-upward bias / multifilament yarn group, or tetraaxial fabrics obtained by stacking a square grid opening fabric woven in plain weave or gauze with warp and weft / multifilament yarn groups with a square grid opening fabric woven in plain weave or gauze with warp and weft / multifilament yarn groups with a 45° left-upward and 45° right-upward bias / multifilament yarn group. Any one of the above, or 4) in the fabrics of 1) to 3) above, one of the biaxial, triaxial, or quaternary fabrics in which the multifilament yarns that are constituent elements are replaced with coated yarns in which the entire outer circumference of the multifilament yarns is coated with a molten resin composition containing one selected from vinyl chloride resin, ethylene vinyl acetate copolymer resin, urethane resin, acrylic resin, and polyvinyl alcohol resin (there are no particular provisions for the amount of impregnation coating), or 5) in which the entire outer circumference of the fabrics of 1) to 3) above is impregnated and coated with a resin composition (vinyl chloride resin paste sol, emulsion resin, heat-melt resin composition, etc.) containing one selected from vinyl chloride resin, ethylene vinyl acetate copolymer resin, urethane resin, acrylic resin, and polyvinyl alcohol resin (there are no particular provisions for the amount of impregnation coating), one of the biaxial, triaxial, or quaternary fabrics in which the entire outer circumference of the fabrics of 1) to 3) above is impregnated and coated with a resin composition (vinyl chloride resin paste sol, emulsion resin, heat-melt resin composition, etc.) containing one selected from vinyl chloride resin, ethylene vinyl acetate copolymer resin, urethane resin, acrylic resin, and polyvinyl alcohol resin (there are no particular provisions for the amount of impregnation coating). In addition to the main resin, the resin compositions described in 4) and 5) above may optionally contain known resin additives in any amount, such as plasticizers, metal composite stabilizers, inorganic flame retardants, bromine-substituted organic compound flame retardants, inorganic fillers, pigments, and weather-resistant stabilizers.Furthermore, the plain weave fabrics described in 1) to 3) above include plain weave fabrics with two warp and weft threads (diagonal weave fabrics), and the gauze weave fabrics are fabrics in which three warp and weft (or bias) threads (left, center, and right) intertwine as strips of warp and weft (or bias) threads, in which case the "left" and "right" of the warp and weft (or bias) threads intertwine in sync, and the "center" of the warp and weft (or bias) threads intertwine to form an interwoven section. The grid-like base materials described in 1) to 5) above are particularly suitable as sheet materials for automatic lifting sheet shutters installed at the entrances and exits of factories and warehouses within factories, and as raw materials (width 1 to 3 m, length 30 to 50 m rolls) for tent structures in outdoor amusement facilities (theme parks, sunshades in event and exhibition venues).

[0017] The grid-like base materials (woven fabrics) described in 1) to 5) above specifically have an area of ​​5 to 100 mm². 2 The open-mesh fabric has voids (approximately square or triangular in shape), and the constituent yarns are multifilament yarns with a fineness of 138 to 1111 dtex (10 to 400 filaments, with the thickness of the fibers varying depending on the spinnability of the synthetic resin constituting the fibers, resulting in a different total number of filaments), preferably used alone or in combination of 2 to 3 yarns (drawn together or twisted together) as one unit. These multifilament yarns can also be optionally treated with dyeing, coloring (dope dyeing using colorants during fiber manufacturing), sizing agent treatment (starch, polymer), water-repellent treatment (perfluoroalkyl group-free copolymer resin), flame-retardant treatment (phosphate ester), etc. In particular, for glass fibers, the surface of the glass fiber can be modified with known silane coupling agents to improve adhesion to the resin coating layer or heat shielding layer. These, for example, use 500 (555 dtex) denier yarn as both warp and weft threads, woven in pairs (1 unit) at a yarn density of 6 units per inch, resulting in a void ratio of 27% and a roughly square void area of ​​5.3 mm². 2 A plain weave (twill weave) fabric, for example, using warp and weft threads consisting of three strands of 750 (832 dtex) denier yarn as one unit, with a yarn density of 4 units per inch, resulting in a void ratio of 28% and a roughly square void area of ​​11 mm². 2For example, using a gauze fabric, with warp and bias threads consisting of three strands of 750 (832 dtex) denier yarn as one unit, and each thread density being three units per inch, the resulting fabric has a void ratio of 25% and a roughly triangular void area of ​​12 mm². 2 Examples include triaxial gauze fabrics. The void ratio is the ratio of the total area of ​​voids to any unit area region of the fabric, and is preferably 20-40%. If the void ratio is less than 20%, the visual effect will be insufficient, and conversely, if it exceeds 40%, there will be insufficient solid areas where stress is applied, which tends to worsen dimensional stability (resistance to deformation) in the warp and weft (or bias) directions. These examples of yarn density and void ratio also apply to yarn density and void ratio for fabrics using coated yarn.

[0018] As the lattice-shaped base material used in the highly light-transmissive insect-proof and heat-insulating sheet of the present invention, the net is also a square lattice net obtained by laminating (such as a non-woven fabric obtained by laminating a weft / yarn-processed multifilament yarn group on a warp / yarn-processed multifilament yarn group, or a non-woven fabric obtained by laminating a weft yarn between two warp yarns) and thermally bonding the 6) warp / yarn-processed multifilament yarn group and the weft / yarn-processed multifilament yarn group, or a three-axis net of a triangular lattice obtained by laminating (such as a non-woven fabric obtained by laminating a left-ascending (or right-ascending) bias / yarn-processed multifilament yarn group with a 30° left-ascending and a 30° right-ascending bias / yarn-processed multifilament yarn group on a warp / yarn-processed multifilament yarn group) and thermally bonding the 7) warp / yarn-processed multifilament yarn group, particularly a left-ascending bias / yarn-processed multifilament yarn group with a 30° left-ascending and a right-ascending bias / yarn-processed multifilament yarn group with a 30° right-ascending, or an axis net including a square lattice / triangular lattice obtained by laminating (such as a non-woven fabric obtained by laminating a weft / yarn-processed multifilament yarn group on a warp / yarn-processed multifilament yarn group, then laminating a left-ascending or right-ascending bias yarn group thereon, and then laminating a right-ascending or left-ascending bias yarn group thereon) using the 8) warp and weft / yarn-processed multifilament yarn group, particularly a left-ascending bias / yarn-processed multifilament yarn group with a 45° left-ascending and a right-ascending bias / yarn-processed multifilament yarn group with a 45° right-ascending. For the resin processing of the lattice-shaped nets of the 6) to 8), it is a net coated with one kind (particularly an aqueous resin) selected from vinyl chloride-based resins, ethylene vinyl acetate copolymer resins, urethane-based resins, acrylic resins, and polyvinyl alcohol resins. The ratio of the mass of the net to the mass of the resin is 10:1 to 1:1, preferably 5:1 to 3:2. The porosity of the lattice-shaped net of the 6) is 70 to 95%, particularly 75 to 90%, and the area of one lattice is 64 mm 2 ~625 mm 2 Within the range, the adjacent interval of the yarns is 8 mm to 25 mm, and the mass is 10 to 75 g / m 2 Can be exemplified. Also, the area of one lattice of the 7) is 70 mm 2 ~500 mm 2 Within the range, the adjacent interval of the yarns is 9 mm to 25 mm, and the mass is 15 to 100 g / m 2 . Also, the area of one triangular lattice of the 8) is 50 mm 2 ~200 mm 2 Within the range, and the area of one square lattice is 100 mm 2 ~1600 mm 2 Within the range (the area of one triangular lattice is 25 mm 2 ~400 mm2 Within this range, the spacing between adjacent threads is 10mm to 40mm, and the mass is 20 to 150g / m². 2 The grid-like base materials (nets) described in 6) to 8) above are particularly suitable for sheet rolls (1-3m wide, 30-50m long) used for pool fences, open terrace awnings / parasols, sunshade enclosures for gardens and orchards, partitions inside factories and research facilities, partitions inside hospitals and medical facilities, partition stalls, etc.

[0019] The fiber type of multifilament yarn used in a lattice-like substrate (woven fabric or net) is one or more multifilaments selected from glass fibers, polyester fibers (including fully aromatic polyester fibers), polyamide fibers (including fully aromatic polyamide fibers), polypropylene fibers, vinylon fibers, carbon fibers, and aromatic heterocyclic polymer fibers (polybenzoxazole, polybenzimidazole, polybenzthiazole) (100 to 500 single filaments with a diameter of 1 to 20 μm are bundled together; for carbon fibers, 1500 to 3000 single filaments with a diameter of 0.3 to 1.5 μm are bundled together). In particular, polyester fibers are preferably polyethylene terephthalate and polyethylene furanoate, and polyamide fibers are preferably melt-spun multifilaments from nylon 6, nylon 6,6, nylon 6,10, furan-based polyamides (polycondensation of alkylenediamine and 2,5-franzicarboxylic acid). The raw material resins for these fibers are preferably those synthesized from fossil fuel-derived monomers, those synthesized from biomass-derived monomers and containing resin, those containing material-recycled resin, and even those containing recycled / regenerated resin, as these align with the objective of carbon neutrality (reducing carbon dioxide emissions, which contribute to global warming). These recycled / regenerated resins (including biomass resins) are preferably polyester resins, which are versatile and widely used. In particular, examples of recycled / regenerated polyester resins include polyesters obtained by decomposing polyethylene terephthalate into monomers such as terephthalic acid, dimethyl terephthalate, bis-2-hydroxyethyl terephthalate, and ethylene glycol, and then repolymerizing ethylene glycol with terephthalic acid, dimethyl terephthalate, bis-2-hydroxyethyl terephthalate, etc.

[0020] The thickness of the heat shielding layer laminated onto the grid-like substrate (woven fabric) is 0.18 mm to 0.6 mm, and the thickness of the heat shielding layer laminated onto the grid-like substrate (net) is 0.12 mm to 0.3 mm. As long as the heat shielding layer is laminated onto at least one side of the grid-like substrate (woven fabric or net), preferably the front side, the back side may be either a heat shielding layer or a non-heat shielding layer, but it is preferable that both the front and back sides are heat shielding layers. It is preferable that the thickness of the non-heat shielding layer is the same as that of the heat shielding layer. Alternatively, the surface side may have a heat shielding layer, and nothing may be laminated on the back side of the grid-like substrate (woven fabric or net). The heat shielding layer and the non-heat shielding layer are made from a thermoplastic resin composition compound such as soft polyvinyl chloride resin, which is formed into a film (sheet) with a thickness of 0.12 mm to 0.6 mm by calendering or T-die extrusion molding. Specifically, the composition of the heat-shielding layer using a flexible polyvinyl chloride resin composition is a compound containing polyvinyl chloride resin (100 parts by mass: 55-60% by mass), plasticizer (40-60 parts by mass: 23-35% by mass), stabilizer for polyvinyl chloride resin (1-5 parts by mass: 0.6-3% by mass), luminous mica particles (1-10 parts by mass: 0.6-6% by mass), pyrethroid compound (1-10 parts by mass: 0.6-6% by mass), and cellulose nanofiber (0.25-3 parts by mass: 0.15-2% by mass), further containing an ultraviolet-excited keto / enol type tautomer (0.3-5 parts by mass: 0.15-3% by mass), and further containing a near-infrared absorbing material (0.2-5 parts by mass: 0.1-3% by mass), and the parts of each compounding agent are not limited to those listed above. In the above, the mass percentage is a simulation of the content ratio relative to the provisional mass of the heat shielding layer, which is approximately 175. The composition of the non-heat shielding layer is the same as the composition of the heat shielding layer, but with the luminous mica particles removed, or with the luminous mica particles and near-infrared absorbing material removed. The lamination of the heat shielding layer and the non-heat shielding layer (optional) onto the grid-like substrate (woven fabric or net) is performed by heat melting and pressing using a laminator having one or two continuous pressing units of heat rolls / rubber rolls, a cooling roll unit, and a winding unit, with one or two passes of the laminator.The thickness of a highly light-transmitting insect-repellent and heat-shielding sheet with a woven fabric grid base (with heat-shielding layers on both sides) is approximately 0.4 to 1.5 mm, and the thickness of a highly light-transmitting insect-repellent and heat-shielding sheet with a net grid base (with heat-shielding layers on both sides) is approximately 0.25 to 0.65 mm. Mass (g / m). 2 ) varies depending on the type of thermoplastic resin used in the heat shielding layer and the type of fiber constituting the lattice-like substrate, so there are no specific regulations.

[0021] Furthermore, regarding the details of each compounding agent, the vinyl chloride resin can be used alone as straight PVC (number average molecular weight 1000-2000) or biomass monomer-derived PVC (number average molecular weight 1000-2000). In addition, these PVCs can be used in combination with modified PVCs such as cross-linked vinyl chloride resin, chlorinated vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, acrylic-(grafted) vinyl chloride copolymer, and urethane-vinyl chloride (grafted) copolymer in a mass ratio of 10:1 to 1:1. Plasticizers that can be used include adipic acid ester compounds (DOA, DINA, DIDA, etc.), phthalate ester compounds (DOP, DINP, DIDP, DUP, etc.), cyclohexanedicarboxylic acid ester compounds, cyclohexenedicarboxylic acid ester compounds, trimellitic acid tris ester plasticizers, pyromellitic acid tetrakis ester plasticizers, aromatic phosphate ester compounds (TCP, CDP, TPP, etc.), chlorinated paraffin compounds, polyester compounds, and synthetic products derived from biomass compounds with the same chemical structure as the listed plasticizers. Stabilizers that can be used include barium-zinc complexes, calcium-zinc complexes, and epoxidized soybean oil (biomass-derived synthetic products). Furthermore, the heat-shielding layer and the non-heat-shielding layer can contain approximately 0.15 to 3% by mass of an ultraviolet-excited keto / enol type tautomer (one or more selected from benzotriazole compounds, triazine compounds, and diphenyl ketone compounds) relative to the mass of the heat-shielding layer. Through molecular motion that reversibly repeats tautomerism between keto and enol types in response to ultraviolet light, ultraviolet energy is converted and released as thermal energy, thereby mitigating the effects of ultraviolet light. At the same time, wavelengths below 380 nm, which are detected by phototactic insects, are cut off, suppressing the attraction of phototactic insects indoors. By including a small amount of a coloring agent (such as a yellow to reddish-brown pigment or dye), a blinding effect is achieved that cuts wavelengths below 480 nm, further suppressing the attraction of phototactic insects indoors. On the other hand, insects with negative phototaxis experience a photoreaction in their compound eyes when exposed to light, creating the illusion of daylight. They then stop moving to avoid being preyed upon by birds. This prevention of attraction due to inactivity is particularly pronounced with yellow light around 570 nm.Furthermore, adhesives (such as polyfunctional isocyanate compounds and silane coupling agents), fungicides (such as imidazole compounds, thiazole compounds, isothiazolino compounds, pyridine compounds, N-haloalkylthio compounds, and phenoxyarsine compounds), antistatic agents, surfactants, antioxidants, and fragrances may be added to the heat-shielding layer and the non-heat-shielding layer, provided that transparency (visibility) is not impaired.

[0022] The lustrous mica particles are scales with an average particle size of 5 to 100 μm, particularly 25 to 75 μm, composed of synthetic mica and a thin film coating layer, with no particular limitations on the aspect ratio. The thin film coating layer is preferably one of the following: a single layer of titanium dioxide, two layers of titanium dioxide / silicon dioxide, or three layers of titanium dioxide / silicon dioxide / titanium dioxide, with an interference color of pearl pink to pearl violet. This coating layer of lustrous mica particles enables the emission of a heat shielding effect through the refraction and reflection of near-infrared rays. The coverage rate of the thin film coating layer is preferably 35 to 70% by mass, particularly 35 to 50% by mass. For example, if it is less than 35%, the near-infrared shielding from sunlight tends to be insufficient, while if it exceeds 70%, the transparency of the sheet tends to decrease. A method for forming the thin film coating layer (titanium dioxide) is, for example, to coat the surface of synthetic mica with titanium hydroxide by hydrolysis of titanium tetrachloride, and then sinter to crystallize the titanium dioxide. Similarly, a method for forming the thin film coating layer (silicon oxide) involves coating the surface of the synthetic mica with silicon hydroxide by hydrolysis of silicon tetrachloride, and then sintering it to crystallize the silicon oxide. The content of lustrous mica particles (1-10 parts by mass: 0.6-6% by mass) in the heat shielding layer is preferably 0.6-6% by mass, considering the balance between light transmission and heat shielding properties. This is 0.6-6 parts by mass per 100 parts by mass of the base thermoplastic resin, or 1-10 parts by mass per 100 parts by mass of the vinyl chloride resin in the case of the base vinyl chloride resin composition. The heat shielding effect of the lustrous mica particles suppresses heat accumulation and temperature rise of the highly light-transmitting insect-repellent heat-shielding sheet itself, and controls the excessive evaporation of pyrethroid compounds (insecticides), enabling long-term sustained and stable release.

[0023] Examples of pyrethroid compounds included in the heat-shielding layer and the non-heat-shielding layer (if a non-heat-shielding layer is present) include empenthrin (also known as vaporthrin: C 18 H 26 O2: Molecular weight 274.4 (Chemical name: 1-ethynyl-2-methyl-2-pentenyl=2,2-dimethyl-3-(2-methyl-1-propenyl)-1-synchropropanecarboxylate), Flamethrin (also known as Pinamin D:C) 18 H 22 O3: Molecular weight 286.4 (Chemical name: 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid 5-propargylfuran-2-ylmethyl), Prallethrin (also known as Ethoc: C) 19 H 24 O3: Molecular weight 300.4 (Chemical name: (+)-2-methyl-4-oxo-3-(2-propynyl)(±)-2-cyclopentenyl(+)-cis / transchrysanthemate), allethrin (also known as pinamine: C) 19 H 26 O3: Molecular weight 302.4 (Chemical name: Dl-3-allyl-2-methylcyclopenta-2-en-4-on-1-yl-DL-cis, transchrysanthemate), imiprothrin (also known as Pral: C) 17 H 22 N2O4: Molecular weight 318.3 (Chemical name: 2,5-dioxo-3-prop-2-inylimidazolidined-1-ylmethyl(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate), pyrethrin (C 21 H 28 O3: Molecular weight 328.4 ("Chemical name: A mixture of pyrethrin I, II, synerin I, II, and jasmolin I, II"), Phthalthrin (also known as Neopinamin: C) 19 H 25 NO4: Molecular weight 331.4 (Chemical name: N-(3,4,5,6-tetrahydrophthalimide)methyl-D,L-cis,transchrysanthemate), resmethrin (also known as Chrislon: C) 22 H 26 O3: Molecular weight 338.5 (Chemical name: (5-benzyl-3-furyl)methyl d-cis,transchrysanthemate), phenothrin (also known as Smithrin: C)23 H 26 O3: Molecular weight 350.4 (Chemical name: 3-phenoxybenzyl d-cis, trans-chrysanthemate), Metofluthrin (also known as Eminence: C) 18 H 20 F4O3: Molecular weight 360.3), Synerin II (C 21 H 26 O5 (molecular weight 360.4), transfluthrin (also known as biothrin: C) 15 H 12 Cl2F4O2: Molecular weight 371.1 (Chemical name: 2,3,5,6-tetrafluorobenzyl=(1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate), Jasmolin II (C 22 H 30 O5: Molecular weight 374.5), Cyphenothrin (also known as Gokilate: C 24 H 25 NO3: Molecular weight 375.5 (Chemical name: Cyano(3-phenoxyphenyl)methyl=2,2-dimethyl-3-(2-methylpropa-1-en-1-yl)cyclopropanecarboxylate), peratrin (C 18 H 21 ClO4: Molecular weight 375.5), etofenprox (C 25 H 28 O3: Molecular weight 376.5 (Chemical name: 2-(4-ethoxyphenyl)-2-methylpropyl=3-phenoxybenzyl ether), monfluorothrin (C 19 H 19 F4O3: Molecular weight 385.3), permethrin (also known as Exmin: C 21 H 20 Cl2O3: Molecular weight 391.3 (Chemical name: 3-phenoxybenzyl = 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate), silafluofen (C 25 H 29 FO2Si: molecular weight 408.6), tefluthrin (C 17 H 17 ClF7O2: Molecular weight 418.7), bifenthrin (C 23 H 22ClF3O2: Molecular weight 422.9 (Chemical name: 2-methyl-1,1'-biphenyl-3-ylmethyl=(Z)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate), and cyfluthrin (also known as bifluthrin: C 22 H 18 One or more compounds selected from Cl2FNO3 (molecular weight 434.3, chemical name: α-cyano(4-fluoro-3-phenoxy)benzyl = 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylate), with a particular preference for the use of two compounds in combination, and a molecular weight difference of 40 to 160 between the two is preferred. Most of these pyrethroid compounds have a chrysanthemum acid structure in their molecular structure, and this chrysanthemum acid structure acts as an insecticide (insecticide, repellent, knockdown).

[0024] The combined use of two pyrethroid compounds is performed with a combined mass ratio of 1:3 to 3:1 and a molecular weight difference of 40 to 160, particularly 60 to 140, in an amount of 1 to 10 parts by mass per 100 parts by mass of vinyl chloride resin, and 0.6 to 6% by mass, preferably 2 to 5% by mass, for the heat-shielding layer and non-heat-shielding layer made of the flexible vinyl chloride resin composition. Alternatively, the amount is 1 to 10 parts by mass per 100 parts by mass of thermoplastic resin, and 1 to 10% by mass, preferably 2 to 5% by mass, for the heat-shielding layer and non-heat-shielding layer made of the thermoplastic resin. This combined use of the two compounds enables a time-delayed effect of rapid action (fast-acting) to residual action (long-lasting effect) in the insecticidal effect (insecticide, repellent, or knockdown). When two pyrethroid compounds are used in combination, with a molecular weight difference of 40-160, and the mass ratio of the smaller pyrethroid compound to the larger pyrethroid compound is 3:1 or close to this (approximately 3:1-5:3), the formulation exhibits primarily rapid action while also having excellent residual effect. On the other hand, when the mass ratio of the smaller pyrethroid compound to the larger pyrethroid compound is 1:3 or close to this (approximately 1:3-3:5), the formulation exhibits primarily residual effect while also having excellent rapid action. If the molecular weight difference is less than 40, the difference between rapid action and residual effect may become unclear. This combined effect of two pyrethroid compounds is particularly pronounced in flexible polyvinyl chloride resins containing 20-40% by mass of a plasticizer (molecular weight 370-475). As synergists that enhance the action of pyrethroid compounds, using 5-[2-(2-butoxyethoxy)]-6-propyl 1,3-benzodioxole, N-(2-ethylhexyl)bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxymide, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]octa-5-ene-2,3-dicarboxymide, octachlorodipropyl ether, etc., in amounts 1 to 10 times the total amount of pyrethroid compounds, inhibits microsomal complex oxidases that metabolize and decompose insecticides in vivo, thereby suppressing the degradation of pyrethroid compounds in insects and thus enhancing the efficacy of the insecticide.Other insect repellent ingredients, depending on the type of pest being targeted (mosquitoes, flies, termites, cockroaches), may be used in combination with pyrethroid compounds in amounts equal to or less than the following: common names: dichlorvos, pyridaphenthion, fenitrothion, fenthion, foxim, diazinon, propethamphos, tetrachlorvinphos, phenobucarb, carbaryl, propoxul, troisan, DEET, icaridin, pyriproxyfen, methoxadiazone, fipronil, hydramethylnon, amidoflumet, clothianidin, acetamiprid, imidacloprid, thiamethoxam, silafluofen, chlorfenapyr, etc.

[0025] The cellulose nanofibers included in the heat-shielding layer and the non-heat-shielding layer (if a non-heat-shielding layer is present) can be either unmodified cellulose nanofibers obtained by mechanical treatment or modified cellulose nanofibers obtained by chemical treatment. The amount of these nanofibers is preferably 0.25 to 3 parts by mass per 100 parts by mass of vinyl chloride resin, and 0.15 to 2% by mass, preferably 0.5 to 1% by mass, for the heat-shielding layer and non-heat-shielding layer made of the flexible vinyl chloride resin composition. Also, the amount is 0.25 to 3 parts by mass per 100 parts by mass of thermoplastic resin, and 0.25 to 3% by mass, preferably 0.5 to 1% by mass, for the heat-shielding layer and non-heat-shielding layer made of thermoplastic resin. If the amount is less than this, the amount of pyrethroid compound supported will be insufficient, and the long-term insect-repellent effect will not be achieved. If the amount is more than this, it tends to impair the transparency of the sheet (visibility to the other side of the sheet). Modified cellulose nanofibers include carboxymethylated cellulose, oxidized cellulose, borate-esterified cellulose, phosphate-esterified cellulose, silicate-esterified cellulose, isocyanate-modified cellulose, aminosilane-modified cellulose, vinylsilane-modified cellulose, epoxysilane-modified cellulose, methacrylicsilane-modified cellulose, acrylicsilane-modified cellulose, chlorosilane-modified cellulose, mercaptosilane-modified cellulose, isocyanurate-silane-modified cellulose, and isocyanate-silane-modified cellulose. By supporting (exhausting) pyrethroid compounds (liquid) onto these cellulose nanofibers, the transparency of the cellulose nanofibers is increased (by suppressing diffuse reflection and changing the refractive index in a wet state), while simultaneously ensuring the transparency of the insect-proof partition sheet and providing the ability to control the sustained release of the pyrethroid compound. The amount of pyrethroid compound supported on the cellulose nanofiber does not need to be the total amount of pyrethroid compound blended; approximately 10-50% by mass of the pyrethroid compound is sufficient. The combination of free pyrethroid compound (immediate sustained release) and cellulose nanofiber-supported pyrethroid compound (long-term sustained release) ensures stable and sustained insecticidal effect from the start of use.In particular, the combined use of two pyrethroid compounds is preferred, with a molecular weight difference of 40 to 160 between the two, and a mass ratio of 1:3 to 3:1 between the pyrethroid compound with the smaller molecular weight and the pyrethroid compound with the larger molecular weight. By using the pyrethroid compound with the smaller molecular weight (it does not need to be fully supported, 10 to 50% by mass is sufficient) to support the cellulose nanofiber, the insect-repellent effect is more stable and sustained. Cellulose nanofibers are single nanofibers (powder, slurry, dispersion liquid) that are produced by mechanically defibrating (coarse defibration, fine defibration) cellulose raw materials (chemically treated pulp, mechanically crushed pulp, recycled paper pulp, etc.) to nanoscale the fiber diameter, with an average aspect ratio (average fiber length / average fiber diameter) of 10 to 50, an average fiber diameter of 3 nm to 100 nm, an average fiber length of 100 μm or less, especially short fibers of 300 nm to 500 nm, and consisting of crystalline, quasi-crystalline, and amorphous parts.

[0026] Modified cellulose nanofibers can be processed using methods such as carboxymethylation, oxidative modification, esterification (one or more selected from borate esterification, phosphoric acid esterification, and silicate esterification), isocyanation, and silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylicsilane modification, acrylicsilane modification, chlorsilane modification, mercaptosilane modification, isocyanuratesilane modification, and isocyanatesilane modification). In particular, carboxymethylation involves carboxymethylating the primary and secondary hydroxyl groups (positions 2,3,6) of cellulose, while oxidative modification involves selectively converting only the primary hydroxyl groups (C6-OH groups) of pulp cellulose to C6-carboxyl group sodium salts using an oxidation catalyst solution containing TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical) catalyst, NaBr, and sodium hypochlorite, resulting in a COOH group content of 0.8 to 1.7 mmol / g. Furthermore, silane coupling agent treatment (modification such as aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylicsilane modification, acrylicsilane modification, chlorsilane modification, mercaptosilane modification, isocyanuratesilane modification, isocyanatesilane modification, etc.) involves treating cellulose nanofibers with an aqueous solution containing one or more silane coupling agents, and the hydrolysate of the silane coupling agent: XR-Si(OH)3 (X = amino group, vinyl group, epoxy group, methacrylic group, acrylic group, chlor group, mercapto group, isocyanurate group, isocyanate group, etc. (R = alkyl chain)) is cellulose nanofiber. This invention relates to one or more reaction products bonded to the hydroxyl groups, carboxyl groups, etc., of cellulose nanofibers. In this invention, by using unmodified cellulose nanofibers or modified cellulose nanofibers (particularly silane coupling agent-treated modified products) and supporting pyrethroid compounds on them, it is possible to impart an effect of controlled sustained release of pyrethroid compounds. When pyrethroid compounds are supported on these, they exhibit particularly excellent affinity with modified cellulose nanofibers, and this affinity allows for stable and controlled sustained release of pyrethroid compounds.

[0027] Examples of silane coupling agents include one or more selected from aminosilane, vinylsilane, epoxysilane, methacrylicsilane, acrylicsilane, chlorsilane, mercaptosilane, isocyanuratesilane, and isocyanatesilane. A silane coupling agent is an alkoxysilane compound represented by the general formula: XR-Si(Y)3, having two or more different reactive groups in the molecule. For example, X = amino group, vinyl group, epoxy group, methacrylic group, acrylic group, chlor group, mercapto group, isocyanurate group, isocyanate group, etc. (R = alkyl chain), Y = methoxy group, ethoxy group, etc. The silane coupling agent hydrolyzes in aqueous solution to produce the general formula: XR-Si(OH)3, and this hydrolysate combines with primary and secondary hydroxyl groups (positions 2, 3, and 6), carboxyl groups, etc. of a cellulose molecule to obtain silane coupling agent-treated cellulose nanofibers. Such bonding is particularly suitable for silane coupling agents such as X = amino group, epoxy group, mercapto group, and isocyanate group.

[0028] As a form of modification by esterification, boric acid esterification involves treating cellulose nanofibers with boric acid such as orthoboric acid (H3BO3) and metaboric acid (HBO2), and borate aqueous solutions such as sodium tetraborate hydrate (Na2B4O7·10H2O) and sodium pentaborate (NaB5O8), causing the boric acid components to react with the hydroxyl groups and carboxyl groups of the cellulose nanofibers. Phosphate esterification involves treating nanocellulose with orthophosphoric acid (H3PO4), pyrophosphoric acid, polyphosphoric acid (HPO3) Modification involves treating cellulose nanofibers with phosphates such as phosphorous acid and phosphinic acid, and phosphate aqueous solutions such as metal salts and ammonium salts derived from these phosphates, reacting the phosphate components with the hydroxyl and carboxyl groups of cellulose nanofibers. Silicate esterification is a modification method in which cellulose nanofibers are treated with silicic acid and silicate aqueous solutions such as sodium silicate (water glass), lithium silicate, and potassium silicate, reacting the silicic acid components with the hydroxyl and carboxyl groups of cellulose nanofibers. When pyrethroid compounds are supported on these modified cellulose nanofibers, they exhibit excellent affinity, and this affinity provides an effect that allows for stable and controlled release of the pyrethroid compounds.

[0029] The UV-excited keto / enol tautomers included in the heat-shielding layer and the non-heat-shielding layer (if a non-heat-shielding layer is present) are one or more selected from benzotriazole tautomers, triazine tautomers, and diphenylketone tautomers, with a mixture of these three (e.g., a mass ratio of 1:1:1, or close to this) being particularly preferred. Keto / enol tautomers are organic compounds in which R2-CH-(C=O)-R1 (keto isomer) and R2-C=CH(OH)-R1 (enol isomer) can be reversibly converted, and both isomers can repeatedly interconvert, resulting in the coexistence of both isomers in equilibrium. These are benzotriazole compounds with a molecular weight in the range of 250 to 700, particularly hydroxyphenylbenzotriazole derivatives as the enol type, and also compounds with a molecular weight of 250 to 700. Triazine compounds in the specified range, particularly enol type, such as hydroxyphenyl-1,3,5-triazine derivatives, and diphenyl ketone compounds in the molecular weight range of 200 to 400, particularly enol type, such as hydroxydiphenyl ketone derivatives, are preferred. The amount of these compounds is preferably 0.3 to 5 parts by mass per 100 parts by mass of vinyl chloride resin, and 0.15 to 3% by mass, preferably 0.5 to 2% by mass, relative to the heat-shielding layer and non-heat-shielding layer made of soft vinyl chloride resin. Also, the amount is 0.3 to 5 parts by mass per 100 parts by mass of thermoplastic resin, and 0.3 to 5% by mass, preferably 0.5 to 2% by mass, relative to the heat-shielding layer and non-heat-shielding layer made of thermoplastic resin. If the amount is too low, the UV removal effect will be poor and the insect-repellent effect and UV degradation prevention effect on pyrethroid compounds will not be exhibited. Conversely, if the amount is too high, a corresponding UV removal effect will not be obtained. By including UV-excited keto / enol tautomers in the heat-shielding and non-heat-shielding layers, the keto / enol tautomers, excited by UV light emitted from a light source or sunlight, repeatedly interconvert between enol and keto isomers in nanoseconds. This UV consumption effect converts UV energy into molecular vibrational energy from the interconversion and releases it outside the system, reducing the amount of wavelengths below 380 nm that penetrate the sheet. As a result, phototactic insects cannot detect wavelengths below 380 nm, thus preventing the attraction of flying insects.Before LEDs, incandescent bulbs and halogen lamps, which emitted ultraviolet light that attracted insects, were the mainstream lighting. However, with the recent shift to LED bulbs and LED fluorescent lamps, which do not emit ultraviolet light or heat, the problem of insect attraction directly caused by the light source has become less severe than before.

[0030] The heat shielding layer contains tungsten oxide, indium oxide, tin-doped indium oxide (ITO: a composite oxide containing approximately 10% by mass of tin oxide (SnO2) in indium oxide (In2O3)), antimony-doped tin oxide (ATO: a composite oxide containing approximately 10% by mass of antimony oxide (Sb2O3) in tin oxide (SnO2)), and cesium-doped tungsten oxide (especially Cs 0.33Preferably, the heat shielding layer contains 0.5 to 10% by mass, particularly 1 to 5% by mass, of one or more near-infrared absorbing materials (particle size of 1 to 80 nm that strongly absorbs wavelengths of 800 nm to 1200 nm) selected from WO3, aluminum-doped zinc oxide (AZO), lanthanum hexaboride (LaB6), phthalocyanine compounds, naphtholquinone compounds, iminium compounds, anthraquinone compounds, aminium compounds, and nickel-thiol complex compounds, and is colored. These near-infrared absorbing materials have high visible light transmittance and excellent solar radiation shielding function, exhibiting a heat shielding effect through synergy with the near-infrared refraction and reflection of luminous mica particles within the same layer. The higher the content of the near-infrared absorbing material, the higher the heat shielding effect, but conversely, it tends to worsen the transparency of the heat shielding layer. In the present invention, the thickness of the heat shielding layer laminated on a grid-like substrate (woven fabric) is 0.18 mm to 0.6 mm, and the thickness of the heat shielding layer laminated on a grid-like substrate (net) is 0.12 mm to 0.3 mm. For example, when the thickness of the heat shielding layer for woven fabric is thin, such as 0.18 mm to 0.22 mm, it is preferable to use a high concentration of near-infrared absorbing material, such as 6 to 8% by mass relative to the mass of the heat shielding layer. Similarly, when the thickness of the heat shielding layer for woven net is thin, such as 0.12 mm to 0.16 mm, it is preferable to use a high concentration of near-infrared absorbing material, such as 8 to 10% by mass relative to the mass of the heat shielding layer. Conversely, when the thickness of the heat shielding layer is thick, it is preferable to adjust the concentration to 0.5 to 4% by mass. The average particle size of these near-infrared absorbing materials is 10 to 10,000 nm, and particles with an average particle size of 50 to 5,000 nm are particularly preferred. The smaller the average particle diameter, the greater the number of particles for the same amount added, resulting in a higher multiple scattering effect due to particle overlap and a high near-infrared reflectance (heat shielding effect). Also, the smaller the average particle diameter, the less the transparency decreases even when dispersed throughout the entire heat shielding layer, resulting in high visible light transmittance (transparency). However, smaller average particle diameters are more prone to aggregation, and uniform dispersion is affected by the type of near-infrared absorbing material, the type of thermoplastic resin in the heat shielding layer, i.e., differences in viscoelasticity during melting. Therefore, from the viewpoint of dispersion efficiency, an average particle diameter of 10 to 500 nm, and particularly 10 to 200 nm, is preferred.Phthalocyanine compounds, naphtholquinone compounds, iminium (also known as imonium or immonium) compounds, anthraquinone compounds, aminium compounds, and nickel-thiol complex compounds are selected from a known group of near-infrared absorption dyes, taking into consideration their hue and maximum absorption wavelength. They can be used individually or in combination of two or more, and are mainly suitable for indoor partitions. The heat shielding effect of these compounds suppresses heat accumulation and temperature rise in the highly translucent insect-repellent heat-shielding sheet itself, and by controlling the excessive evaporation of pyrethroid compounds (insecticides), long-term sustained release and stable operation are possible.

[0031] A fouling-resistant layer is provided on top of a heat-reflective layer (containing luminous mica particles but not near-infrared absorbing materials). This fouling-resistant layer contains 1 to 20% by mass, particularly 3 to 10% by mass, of one or more near-infrared absorbing materials (particle size of 1 to 50 nm that strongly absorbs wavelengths of 800 nm to 1200 nm) selected from tungsten oxide, indium oxide, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO), aluminum-doped zinc oxide (AZO), and lanthanum hexaboride (LaB6), based on the mass of the fouling-resistant layer, preferably so that the fouling-resistant layer possesses both fouling resistance and heat shielding properties. By forming a fouling-resistant layer on top of a heat-reflective layer, the sustained release of pyrethroid compounds becomes the main activity on the back side of the highly translucent insect-repellent heat-shielding sheet, and the sustained release of pyrethroid compounds also begins from the fouling-resistant layer with a large time difference, allowing for longer-lasting repellency, insecticidal effects, and knockdown. These heat-shielding effects suppress heat accumulation and temperature rise in the highly translucent insect-repellent heat-shielding sheet itself, and control the excessive evaporation of pyrethroid compounds (insecticides), enabling long-term, stable sustained release. The antifouling layer can be applied and dried by gravure coating of paints such as acrylic resin, fluoropolymer resin, acrylic-silicone copolymer resin, acrylic-fluoropolymer resin, acrylic-urethane copolymer resin, or a blend of acrylic resin and fluoropolymer resin to form a coating film of, for example, 5 to 50 μm, or by laminating a multilayer film such as a fluoropolymer film or a fluoropolymer / acrylic resin layer with adhesive or by thermal melting to a thickness of, for example, 35 to 80 μm. Furthermore, a photocatalytic layer containing photocatalytic inorganic materials (e.g., photocatalytic titanium dioxide, photocatalytic tungsten oxide, etc.) can also be provided on these antifouling layers.

[0032] Furthermore, the heat-shielding layer and the non-heat-shielding layer contain colorants as needed, making them yellow to reddish-brown and transparent (visible) to absorb and cut wavelengths of 400-480 nm, thereby suppressing the attraction of phototactic insects (moths, flies, mosquitoes, etc.). In addition, for non-phototactic insects such as nocturnal moths, yellow light at 570 nm (1 lux or more) tricks nocturnal moths into thinking it is daytime, when the risk of predation is high, thus inducing cessation of activity or repellent behavior to avoid predation. For the yellow coloring, yellow to orange colors obtained by using pigments such as monoazo yellow, disazo yellow, condensed azo yellow, nickel azo yellow, isoindoline yellow, isoindolinone yellow, naphthol yellow, and quinophthalone yellow, either alone or in combination, are preferred. Furthermore, orange to reddish-brown coloring is achieved by using red pigments in combination with these yellow pigments. Preferred red pigments include azo lake red, monoazo red (Ca-based or Ba-based), condensed azo red, (dimethyl)quinacridone red, diketopyrrolopyrrole red, thioin digomagenta, perylene red, perinone red, anthraquinonyl red, and quinacridone violet. In the specifications of heat shielding layer (front) / lattice substrate / heat shielding layer (back) and heat shielding layer (front) / lattice substrate / non-heat shielding layer (back), it is possible to have both the front and back colored, only one of the front or back colored, or different colorings applied to the front and back. In particular, the combination of this coloring system and the UV-excited keto / enol type tautomer in the heat-shielding and non-heat-shielding layers reduces the transmission of wavelengths below 480 nm, making it difficult for insects to sense wavelengths below 480 nm and thus preventing the attraction of phototactic insects.

[0033] The openings of the retractable sheet shutters can accommodate properties with dimensions of approximately 1m to 10m in width and 2m to 6m in height. For example, for an opening of 3.6m in width and 2.3m in height, three pieces of highly translucent insect-proof and heat-shielding sheet, each 0.8m wide and 3.6m long, are used. The length of the sheet corresponds to the opening width, and the height corresponds to the width of the sheet. The three pieces of sheet are then joined together with a 5cm overlap welding to expand the opening. For a curtain-style curtain, strips of approximately 10cm to 30cm in width and 2m to 6m in height are used in quantities corresponding to the opening size. When the curtain is closed, it is preferable to arrange the strips so that their edges overlap by 1cm to 3cm. The retractable sheet shutters open and close automatically via sensor detection for entry and exit. Curtain-style curtains are used by people, conveyors, or forklifts pushing them aside to enter and exit. Tent structures, open terrace awnings, and parasols are constructed by attaching sewn sheets of raw material to a frame (beam) structure. The length, number, and shape of the raw material sheets can be freely designed according to the scale and design of the tent structure, and these are mainly permanent installations. Sunshades for gardens and orchards, partitions inside factories and research facilities, partitions inside hospitals and medical facilities, and partitioned stalls are made from sewn or cut raw material sheets and can be freely used to divide, block, enclose on four or three sides, cover, hide, etc. These may be permanent or temporary installations.

[0034] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluation items and evaluation methods in the following examples and comparative examples are as follows. 1) Insect repellent effect against flying insects (KT50 / second) Test 1-1 A 6cm x 6cm square sheet is placed in a glass petri dish with a diameter of 8.5cm and a height of 2.5cm, and the dish is covered with a lid and left to acclimate to a 25°C environment for 30 minutes. Ten adult midges are released into this petri dish, and the number of knocked-down midges is counted from this point. The time (in seconds) when half (50%) of the midges are knocked down (5th midge) is determined as "KT50 / second," and the smaller this value (average of 3 tests), the higher the insect repellent effect. *KT50 / sec = Median knock-down time (the time required for 50% of the test insects to become incapacitated (unable to get up, regardless of whether they are alive or dead)). Test 1-2 The sheet pieces from Test 1 above are left in a gear oven at 50°C for 100 days, 125 days, and 150 days. The same test as in Test 1 is repeated using these partition sheet pieces to determine the "KT50 value" of the repellent effect against midges. The smaller this value (average of the three tests), the higher the insect-repellent effect. 2) Repellent effect against clothing pests (KT50) Test 2 Ten adult midges are released into a 30cm (width) x 30cm (depth) x 30cm (height) box made of transparent acrylic (one side is not covered with acrylic), and a 30cm x 30cm sheet is attached to seal the box. The box is placed in a dark room with the sheet-attached side facing the back, and a 60W incandescent light bulb is placed 50cm behind the sheet-attached side and turned on for 30 seconds to create a lantern-like effect, and the number of midges that gather on the sheet surface is counted. 3) UV shielding rate (UV consumption due to heat conversion) Using a V-670 spectrophotometer (manufactured by JASCO Corporation), the ultraviolet transmittance from 280 to 400 μm was measured in accordance with JIS R3106 and calculated according to formula (1). UV shielding (heat conversion) rate (%) = 100% - UV transmittance (%) ... (1) Furthermore, the UV shielding performance was evaluated in three stages based on the UV shielding (heat conversion) rate, as shown below. UV protection (heat conversion) rate class 95% or more 1 90% or more but less than 95% 2 Less than 90% 3 4)Visible light transmittance The visible light transmittance of the film material was measured using a spectroscopic colorimeter CM-3600d (manufactured by Konica Minolta, Inc.) in accordance with JIS Z8722. Furthermore, the light transmittance of the film material was evaluated in three stages as follows based on the visible light transmittance. Visible light transmittance class 40%~80% 1 30% or more but less than 40% 2 Less than 30% 3 5) Heat shielding rate Using an infrared lamp, the percentage of radiant heat shielded by the sheet was measured according to the following test environment and test method. Test Environment: An incandescent lamp (100V, 500W photoreflector lamp: for daylight color: Toshiba Corporation) is installed in the center of the ceiling of a box-shaped structure with internal dimensions of 45cm high x 35cm wide x 35cm long, which has both ambient temperature barrier and airtightness, to constitute a test environment for evaluating heat shielding performance. An external box-shaped frame with external dimensions of 5cm high x 10cm wide x 15cm long is assembled using acrylic resin square rods with a cross-sectional area of ​​0.5cm x 0.5cm as beams. Test sheets are fixed to the four sides, top, and bottom of the box-shaped frame with their surfaces facing outwards to prepare an airtightness test box. In addition, a heat flow meter (Shothrm HFM heat flow meter: manufactured by Showa Denko K.K.) sensor is installed in the center of the bottom of the inside of this test box. A test box covered with a test sheet (example, comparative example) (a blank box without the test film material attached) is mounted to the center of the bottom surface of a box-shaped structure, and fixed so that the direction of the line connecting the center point of the lamp and the center point of the test box coincides vertically. The distance from the tip of the lamp to the ceiling of the test box inside this box-shaped structure is 35 cm. This box-shaped structure is placed in a constant temperature room at 20°C. Test method: Place a test box without a test sheet inside a box-shaped structure and seal it. Turn on the lamp and measure the heat flow rate (kcal / m³). 2 The heat flow rate qn(kcal / m³) after 30 minutes was measured every minute. 2 Measure the heat flow rate (kcal / m³). After returning the temperature inside the box-shaped structure to 20°C, the same as the constant temperature room, place the test box with the test sheet attached inside the box-shaped structure and seal it, turn on the lamp and measure the heat flow rate (kcal / m³). 2 The heat flow rate (qc) is measured every minute, and the heat flow rate after 30 minutes is measured at kcal / m³. 2 h) was measured and calculated according to equation (2). Heat shielding rate (%) = [(qn - qc) / qn] × 100 ... (2) Furthermore, the heat shielding properties of the film material are evaluated in three stages based on the heat shielding rate, as described below. Heat shielding rate class 30% or more 1 20% or more but less than 30% 2 Less than 20% 3

[0035] [Example 1] <Lattice base material (1)> This net uses 1000 denier (1111 dtex) polyethylene teretale (PET) multifilament yarn (192 filaments) that has been impregnated with an acrylic resin emulsion to create untwisted yarn (1.2 mm wide) for both the warp and weft. The weft yarns are placed at 2 cm intervals, and the warp yarns are placed on top of them at 2 cm intervals. The intersections of the yarns are fused and fixed by heat pressing, resulting in a non-woven square grid net (10 g / m²) with a weave density of 1.27 threads / inch and a void ratio of 88%. 2 ) was used. <Partition sheet> Using this square grid net as a base material, a 0.15 mm thick calendered film made of the flexible polyvinyl chloride resin composition [Formulation 1] described below is applied to both sides as a front and back flexible polyvinyl chloride resin coating layer, and then melt laminated by heat compression using a laminator to a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (1) was obtained. [Formulation 1]: Flexible polyvinyl chloride resin composition (compound) 100 parts by mass of polyvinyl chloride resin (degree of polymerization 1300) Diisononyl phthalate (plasticizer: DINP) 22 parts by mass Diphenyl cresyl phosphate (flame retardant plasticizer: CDP) 20 parts by mass Epoxy soybean oil (plasticizer and stabilizer) 3 parts by mass Barium / zinc composite stabilizer, 2 parts by mass Photoluminescent mica particles 3 parts by mass Cesium-doped tungsten oxide (CWO) 0.5 parts by mass Permethrin (pyrethroid compound: Mw391.3) 5 parts by mass Borate-esterified modified cellulose nanofiber (powder) 1.5 parts by mass UV-excited keto / enol type tautomer (benzotriazole type) 0.8 parts by mass UV-excited keto / enol type tautomer (triazine type) 0.8 parts by mass UV-excited keto / enol type tautomer (diphenyl ketone system) 0.8 parts by mass *Luminous mica particles: Particle size 25-65 μm, coverage by TiO2 / SiO2 / TiO2 Interference color pearl pink with a 45% by mass thin film coating layer. *Cesium-doped tungsten oxide (Cs 0.33 WO3) Particle size 50-80 nm *Borate-esterified cellulose nanofibers are 3% boric acid by mass + 78% esterified cellulose nanofibers by mass. Aqueous solution of tilcellosolve is used with carboxymethylated cellulose nanofibers (cellulose). The primary and secondary hydroxyl groups (positions 2, 3, and 6) are carboxymethylated to the carboxymethyl group. Modified material after reaction: Fiber width 3-10 nm: Fiber length 30-100 μm *Borate-esterified cellulose nanofiber (powder) is diisononyl phthalate. (Used by dispersing in plasticizer: DINP) *Benzotriazole tautomer The enol type is a benzene ring with a hydroxyl group (1) at position 2 and a ketone group (0) at position 5 (tert-butyl). The CN bond between one carbon atom at position 1 (a nucleotide group) and a benzotriazole ring (unsubstituted) is formed. MW267 is an organic compound, and its keto form has hydroxyl groups (0) / 2-ketone group (1) as its ben form. A zen ring (5-position tert-butyl group) with one carbon atom at position 1, and a benzotriazole ring (unsubstituted). In the CN compound (MW267), positions 1, 2, and 5 represent the positions of the carbon atoms in the benzene ring. *Triadine tautomer The enol type is a benzene ring with a hydroxyl group (1) at position 2 and a ketone group (0) at position 4 (butoxy). (Base) CC bonds formed by three carbon atoms at position 1 and carbon atoms at positions 2, 4, and 6 of the 1,3,5-triazine ring. MW367 is an organic compound formed by combination, and the keto form has 0 hydroxyl groups and 1 ketone group at position 2. The benzene ring (butoxy group at position 4) has three carbon atoms at position 1, and the 1,3,5-triazine ring CC conjugate (MW367) with carbon atoms at positions 2, 4, and 6, where positions 1, 2, and 4 are benzene rings. The positions of carbon atoms are shown; the 2nd, 4th, and 6th positions of the triazine ring represent the carbon atoms, while the 1st, 3rd, and 5th positions represent nitrogen atoms. Represents the position of N *Diphenyl ketone tautomer The enol form has one hydroxyl group at position 2, zero ketone groups, and one octoxy group at position 4. The carbon at position 1 of one benzene ring (without other substituents) and the benzene ring (without other substituents) MW296 is an organic compound with a C=O interposed bond, and the keto form has hydroxyl groups (0) / position 2- One benzene ring (no other substituents) with one ketone group and one octoxy group at position 4. The carbon at position 1 and the benzene ring (without other substituents) are bonded via a C=O bond (MW296). The 1st, 2nd, and 4th positions represent the positions of carbon atoms in the benzene ring.

[0036] [Example 2] The same procedure as in Example 1 was followed, except that [Formulation 1] was changed to [Formulation 2], resulting in a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (2) was obtained. Formula 2 has the same composition as Formula 1, except that the pyrethroid compound (permethrin) is changed to 4 parts by mass, 1.5 parts by mass of borate-esterified cellulose nanofiber (powder) is changed to 2.5 parts by mass of borate-esterified cellulose nanofiber (exhausted powder) supporting 1 part by mass of permethrin, and 0.5 parts by mass of cesium-doped tungsten oxide (CWO) is changed to 0.5 parts by mass of antimond-doped tin oxide ATO (a composite oxide with a particle size of 50-80 nm containing approximately 10% by mass of antimony oxide Sb2O3 in tin oxide SnO2). Permethrin was supported by blending borate-esterified cellulose nanofiber powder with permethrin (liquid) and exhausting it at room temperature and pressure for 24 hours. 100 g of the permethrin support was prepared, and 2.5 parts by mass were used from it.

[0037] [Example 3] The same procedure as in Example 1 was followed, except that [Formulation 1] was changed to [Formulation 3], resulting in a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (3) was obtained. [Formulation 3] has the same composition as [Formulation 1] except that the pyrethroid compound (permethrin) is changed to 2.5 parts by mass, and a new pyrethroid compound (phenothrin: Mw350.4) is added to create a 1:1 mass ratio combination of the two pyrethroid compounds (molecular weight difference of 41). Furthermore, 0.5 parts by mass of cesium-doped tungsten oxide (CWO) is changed to 0.5 parts by mass of tin-doped indium ITO (a composite oxide with a particle size of 50-80 nm containing approximately 10% by mass of tin oxide SnO2 in indium oxide In2O3).

[0038] [Example 4] The same procedure as in Example 1 was followed, except that [Formulation 3] was changed to [Formulation 4], resulting in a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (4) was obtained. Formula 4 has the same composition as Formula 3, except that the pyrethroid compound (phenothrin) is changed to 1.5 parts by mass, 1.5 parts by mass of borate-esterified cellulose nanofiber (powder) is changed to 2.5 parts by mass of borate-esterified cellulose nanofiber (exhausted powder) supporting 1 part by mass of phenothrin (Mw350.4), and 0.5 parts by mass of cesium-doped tungsten oxide (CWO) is changed to 0.5 parts by mass of lanthanum hexaboride (LaB6: particle size 50-80 nm). The phenothrin was loaded by blending borate-esterified cellulose nanofiber powder with phenothrin (liquid) and exhausting it at room temperature and pressure for 24 hours. 100 g of the phenothrin load was prepared, and 2.5 parts by mass were used from it.

[0039] [Example 5] In Example 1, the grid-like substrate (1: net) was changed to a grid-like substrate (2: woven fabric), and the 0.15 mm thick calendered film made of the flexible polyvinyl chloride resin composition of [Formulation 1] was changed to a 0.22 mm thick calendered film, resulting in a thickness of 0.66 mm and a mass of 818 g / m². 2 The procedure was the same as in Example 1, except that a highly light-transmitting insect-repellent and heat-shielding sheet (5) was used. <Lattice base material (2)> A square grid-like open-mesh fabric (33% void ratio; mass 125g / m²) woven using polyester (polyethylene terephthalate) multifilament yarn (750 denier) as both warp and weft threads, with a warp thread density of 15 threads / inch and a weft thread density of 15 threads / inch. 2 The material was impregnated with the resin described in [Formulation 5] below using a dipping method, dried at 150°C for 1 minute, and then heat-treated at 185°C for 1 minute, resulting in a mass of 234 g / m². 2 A substrate with a porosity of 30% was used. [Formulation 5]: Flexible polyvinyl chloride resin composition (paste) 100 parts by mass of polyvinyl chloride resin (degree of polymerization 1700) Diisononyl phthalate (plasticizer: DINP) 60 parts by mass Epoxy soybean oil (plasticizer and stabilizer) 5 parts by mass Barium / zinc composite stabilizer, 2 parts by mass Zinc stearate (metal soap) 0.8 parts by mass Antimony trioxide (flame retardant) 15 parts by mass Carbon black (modified black pigment) 2 parts by mass

[0040] [Example 6] The grid-like substrate (1) of Example 2 is changed to the grid-like substrate (2) of Example 5, and the 0.15 mm thick calendered film made of the flexible polyvinyl chloride resin composition of [Formulation 2] is changed to a 0.22 mm thick calendered film, resulting in a thickness of 0.66 mm and a mass of 818 g / m². 2 The procedure was the same as in Example 2, except that a highly light-transmitting insect-repellent and heat-shielding sheet (6) was used.

[0041] [Example 7] The grid-like substrate (1) of Example 3 is changed to the grid-like substrate (2) of Example 5, and the 0.15 mm thick calendered film made of the flexible polyvinyl chloride resin composition of [Formulation 3] is changed to a 0.22 mm thick calendered film, resulting in a thickness of 0.66 mm and a mass of 818 g / m². 2 The procedure was the same as in Example 3, except that a highly light-transmitting insect-repellent and heat-shielding sheet (7) was used.

[0042] [Example 8] The grid-like substrate (1) of Example 4 is changed to the grid-like substrate (2) of Example 5, and the 0.15 mm thick calendered film made of the flexible polyvinyl chloride resin composition of [Formulation 4] is changed to a 0.22 mm thick calendered film, resulting in a thickness of 0.66 mm and a mass of 818 g / m². 2 The procedure was the same as in Example 4, except that a highly light-transmitting insect-repellent and heat-shielding sheet (8) was used.

[0043] [Example 9] In Example 1, the soft polyvinyl chloride resin composition (compound) was prepared as follows, except that the composition [Formulation 1] was modified as follows: 3 parts by mass of luminous mica particles (particle size 25-65 μm, interference color pearl pink with a thin film coating layer of TiO2 / SiO2 / TiO2 with a coverage of 45% by mass) was replaced with 3 parts by mass of luminous mica particles (particle size 25-65 μm, interference color pearl violet with a thin film coating layer of TiO2 / SiO2 with a coverage of 45% by mass), 1.5 parts by mass of borate-esterified cellulose nanofiber (powder) was replaced with 1.5 parts by mass of oxidative-modified cellulose nanofiber (powder), and 5 parts by mass of permethrin (pyrethroid compound: Mw391.3) was replaced with 5 parts by mass of allethrin (pyrethroid compound: Mw302.4). The result was a soft polyvinyl chloride resin composition (compound) with a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (9) was obtained. *Oxidation-modified cellulose nanofibers are TEMPO(2,2,6,6-tetramethylpiperium An oxidation catalyst solution containing a din-1-oxy radical catalyst, NaBr, and sodium hypochlorite is used. Furthermore, only the primary hydroxyl groups (C6-OH groups) of cellulose in pulp are selectively treated as C6-carboxyl groups. Converted to a sodium base salt with a COOH group content of 0.8-1.7 mmol / g, resulting in a fiber width of 3-10 nm: Fiber length: 30-100 μm *Oxidation-modified cellulose nanofiber (powder) contains diisononyl phthalate (plasticizer: DIN Distributed and used in P)

[0044] [Example 10] In Example 9, the pyrethroid compound (allethrin) in [Formulation 6] was changed to 4 parts by mass, and 1.5 parts by mass of oxidatively modified cellulose nanofiber (powder) was changed to 2.5 parts by mass of oxidatively modified cellulose nanofiber (exhausted powder) supporting 1 part by mass of allethrin. Except for these changes, the composition was the same as [Formulation 6], and this was designated as [Formulation 7]. A thickness of 0.3 mm and a mass of 400 g / m² were obtained. 2A highly light-transmitting insect-repellent and heat-shielding sheet (10) was obtained. The allethrin support was prepared by blending oxidatively modified cellulose nanofiber powder with allethrin (liquid) and allowing it to be absorbed at room temperature and pressure for 24 hours. 100 g of the allethrin support was prepared, and 2.5 parts by mass were used from it.

[0045] [Example 11] In Example 9, the pyrethroid compound (allethrin) in [Formulation 6] was changed to 2.5 parts by mass, and a new pyrethroid compound (cyfluthrin: Mw434.3) was added at 2.5 parts by mass, resulting in a 1:1 mass ratio combination of the two pyrethroid compounds (molecular weight difference 132). Except for this change, the composition was the same as [Formulation 6], and this was designated as [Formulation 8]. The thickness was 0.3 mm and the mass was 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (11) was obtained.

[0046] [Example 12] In Example 11, the pyrethroid compound (allethrin) in [Formulation 8] was changed to 1.5 parts by mass, and 1.5 parts by mass of oxidatively modified cellulose nanofiber (powder) was changed to 2.5 parts by mass of oxidatively modified cellulose nanofiber (exhausted powder) supporting 1 part by mass of allethrin (Mw302.4). Except for these changes, the composition was the same as [Formulation 8], and this was designated as [Formulation 9], with a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (12) was obtained. The allethrin support was prepared by blending oxidatively modified cellulose nanofiber powder with allethrin (liquid) and allowing it to be absorbed at room temperature and pressure for 24 hours. 100 g of the allethrin support was prepared, and 2.5 parts by mass were used from it.

[0047] [Example 13] The following material was obtained in the same manner as in Example 1, except that [Formulation 10] was used, which was obtained by omitting 0.5 parts by mass of cesium-doped tungsten oxide (CWO) from [Formulation 1] of Example 1. The result was a material with a thickness of 0.3 mm and a mass of 400 g / m². 2 The fluoropolymer paint of [Formulation 11] described below is applied to the surface side of the sheet using a 100-mesh gravure roll, heated and dried in a 120°C hot air oven for 2 minutes, and the fluoropolymer paint of [Formulation 11] is cured to form an antifouling layer (4g / m²). 2A highly light-transmitting insect-repellent and heat-shielding sheet (13) was obtained. The heat-shielding properties (heat shielding) of the obtained highly light-transmitting insect-repellent and heat-shielding sheet (13) were equivalent to those of the highly light-transmitting insect-repellent and heat-shielding sheet (1), and it was found to be excellent in terms of the ease of wiping away dirt adhering to the surface. By adding an anti-fouling layer, it was also found to have excellent long-term sustained release properties of insecticides, such as long-term retention of pyrethroid compounds, for example, a sustained effect approximately 1.4 times longer than that of the highly light-transmitting insect-repellent and heat-shielding sheet (1). [Formulation 11] Fluorine-based resin paint (for forming an anti-fouling layer) 100 parts by mass of hydroxyl group-containing fluoroolefin vinyl ether copolymer (fluorine-based resin) Hexamethylene diisocyanate isocyanurate trimer (isocyanate) 10 parts by mass Cesium-doped tungsten oxide (CWO) 1 part by mass Colloidal silica (antistatic) 8 parts by mass Triazine tautomer (ultraviolet absorber) 5 parts by mass Curing catalyst: Dibutyltin dilaurate (approximately 10 ppm relative to fluororesin) Toluene / butyl acetate (diluent in a 1:1 mass ratio) 400 parts by mass

[0048] [Table 1]

[0049] [Table 2]

[0050] [Table 3]

[0051] Examples 1 and 5 are systems in which permethrin compounds and cellulose nanofibers simply coexist; Examples 2 and 6 are systems in which permethrin compounds and cellulose nanofibers supporting permethrin compounds coexist; Examples 3 and 7 are systems in which two types of permethrin compounds (molecular weight difference 41 and 132) and cellulose nanofibers simply coexist; and Examples 4 and 8 are systems in which two types of permethrin compounds (molecular weight difference 41 and 132) and cellulose nanofibers supporting the permethrin compound (the one with the lower molecular weight) coexist. It was found that Examples 2, 4, 6, and 8, in which a portion of the permethrin compound was supported on cellulose nanofibers, exhibited superior insecticidal effect duration (shorter KT50 seconds at 150hr) compared to Examples 1, 3, 5, and 7, in which permethrin compounds and cellulose nanofibers simply coexisted. Furthermore, Examples 3 and 7, which used two types of permethrin compounds with different molecular weights in combination, showed superior duration of insect-repellent effect compared to Examples 1 and 5, which used only one type of permethrin compound (shorter KT50 seconds at 150hr). Similarly, Examples 4 and 8, in which a portion of the permethrin compound was supported on cellulose nanofibers, also showed superior duration of insect-repellent effect compared to Examples 2 and 6, which used only one type of permethrin compound (shorter KT50 seconds at 150hr). In particular, the action of the UV-excited keto / enol type tautomer contained in the heat shielding layer of the highly light-transmitting insect-repellent heat-shielding sheets of Examples 1 to 12, which converts ultraviolet light into heat and consumes it, eliminated wavelengths shorter than 480nm, thus demonstrating an attraction-suppressing effect on phototactic insects. Furthermore, the highly light-transmitting insect-repellent and heat-shielding sheets of Examples 1 to 12 contain luminous mica particles with a "titanium dioxide / silicon dioxide" thin film coating layer and luminous mica particles with a "titanium dioxide / silicon dioxide / titanium dioxide" thin film coating layer in the heat-shielding layer. This allows them to exhibit a heat-shielding effect through heat reflection while maintaining high visible light transmittance, thereby suppressing heat accumulation and temperature rise of the highly light-transmitting insect-repellent and heat-shielding sheet itself, and controlling the excessive evaporation of pyrethroid compounds (insecticides), enabling long-term sustained and stable release.Due to its combined insect-repellent effect, light transmission / visibility (visible light transmittance), and heat-shielding effect, it has been confirmed to be suitable for use in retractable sheet shutters at factory and warehouse entrances, tent structures for outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, etc.), open terrace awnings and parasols, sunshade enclosures for gardens and orchards, partitions inside factories and research facilities, partitions inside hospitals and medical facilities, partitioned stalls, and more. Furthermore, omitting 0.5 parts by mass of cesium-doped tungsten oxide (CWO) from the heat shielding layers of Examples 1, 5, and 9, similarly omitting 0.5 parts by mass of antimond-doped tin oxide (ATO) from the heat shielding layers of Examples 2, 6, and 10, similarly omitting 0.5 parts by mass of tin-doped indium oxide (ITO) from the heat shielding layers of Examples 3, 7, and 11, and similarly omitting 0.5 parts by mass of lanthanum hexaboride (LaB6) from the heat shielding layers of Examples 4, 8, and 12 will reduce the heat shielding rate of the highly translucent insect-repellent heat shielding sheet to a "Class 2" rating. However, this reduction can be compensated for by increasing the amount of luminous mica particles, as long as it does not impede the visible light transmittance.

[0052] [Comparative Example 1] The composition was the same as in Example 1, except that 1.5 parts by mass of borate-esterified modified cellulose nanofiber was omitted from [Composition 1] of Example 1, resulting in a thickness of 0.3 mm and a mass of 400 g / m². 2 A highly light-transmitting insect-repellent and heat-shielding sheet (14) was obtained. The heat-shielding properties and initial insect-repellent effect were equivalent to the highly light-transmitting insect-repellent and heat-shielding sheet (1) of Example 1, but the omission of cellulose nanofibers resulted in a halving of the sustained effect of the pyrethroid compound. In other words, it is clear from the comparison with Comparative Example 1 that the presence of cellulose nanofibers extends the insect-repellent effect of the conventional insect-repellent formulation.

[0053] [Comparative Example 2] The composition was the same as in Example 1, except that 3 parts by mass of luminous mica particles and 0.5 parts by mass of cesium-doped tungsten oxide (CWO) were omitted from [Composition 1] of Example 1. The result was a thickness of 0.3 mm and a mass of 400 g / m². 2A highly light-transmitting insect-repellent and heat-shielding sheet (15) was obtained. The initial insect-repellent effect was equivalent to that of the highly light-transmitting insect-repellent and heat-shielding sheet (1) of Example 1. However, because the luminous mica particles and cesium-doped tungsten oxide were omitted, a sufficient heat-shielding effect could not be obtained. The highly light-transmitting insect-repellent and heat-shielding sheet itself accumulated heat and its temperature rose, causing excessive evaporation of the pyrethroid compound (insecticide), and preventing long-term sustained release and stable duration.

[0054] [Comparative Example 3] The composition is the same as in Example 1, except that 1.5 parts by mass of borate-esterified cellulose nanofiber is omitted from [Composition 1] of Example 1 and replaced with 1.5 parts by mass of silica (amorphous porous synthetic silica with a pore size of 210 Å and an average particle diameter of 1.4 μm). The result is a material with a thickness of 0.3 mm and a mass of 405 g / m². 2 An insect-repellent and heat-shielding sheet (16) was obtained. The obtained sheet (16) was equivalent to the highly light-transmitting insect-repellent and heat-shielding sheet (1) of Example 1 in terms of heat shielding and initial insect-repellent effect, but due to the effect of replacing cellulose nanofibers with silica, the visibility (visible light transmittance) was inferior, and the long-term sustained release effect of pyrethroid compounds was reduced, and the difference from the adsorption sustained release effect of cellulose nanofibers was clear.

[0055] [Comparative Example 4] The composition is the same as in Example 1, except that 1.5 parts by mass of borate-esterified modified cellulose nanofiber is omitted from [Composition 1] of Example 1 and replaced with 1.5 parts by mass of β-cyclodextone (7 glucose molecules, molecular weight 1135, cavity diameter 0.7-0.8 nm, cavity depth 0.7-0.8 nm). The result is a thickness of 0.3 mm and a mass of 405 g / m². 2 An insect-repellent heat-shielding sheet (27) was obtained. The obtained insect-repellent heat-shielding sheet (17) was equivalent to the highly translucent insect-repellent heat-shielding sheet (1) of Example 1 in terms of heat shielding properties and initial insect-repellent effect. However, due to the effect of replacing cellulose nanofibers with silica, it became cloudy and lost visibility, and the long-term sustained-release effect of pyrethroid compounds was reduced, and the difference from the adsorption sustained-release effect of cellulose nanofibers was clear.

[0056] [Table 4] [Industrial applicability]

[0057] This invention provides a highly translucent, insect-repellent, heat-shielding sheet that is transparent (allows visibility to the other side of the sheet) and combines heat-shielding and insect-repellent properties. It enables the provision of a highly translucent, insect-repellent, heat-shielding sheet that provides stable and sustainable insect-repellent effects against flying insects such as moths, flies, and mosquitoes in extremely hot environments where heat shielding is required. By providing this highly translucent, insect-repellent, heat-shielding sheet, the insect-repellent effect in extremely hot environments is sustained, enabling a wide range of applications such as retractable sheet shutters at factory and warehouse entrances, outdoor amusement facilities (theme parks, sunshades in event and exhibition venues, tent structures, etc.), pool fences, open terrace awnings and parasols, sunshade enclosures for gardens and orchards, partitions in factories and research facilities, partitions in hospitals and medical facilities, and partitioned stalls. Furthermore, by extending the product lifecycle, the waste of resources required for manufacturing partition sheets is reduced, contributing to the reduction of greenhouse gas emissions.

Claims

1. A laminated sheet comprising a heat-shielding layer provided on at least one surface of a grid-like substrate which is a woven fabric or net, wherein the heat-shielding layer contains at least luminous mica particles and a pyrethroid compound / cellulose nanofiber composite, and the pyrethroid compound / cellulose nanofiber composite contains cellulose nanofibers that have adsorbed a portion of the pyrethroid compound, characterized in that it is a highly light-transmitting insect-repellent and heat-shielding sheet.

2. The highly light-transmitting insect-repellent and heat-shielding sheet according to claim 1, wherein the luminous mica particles are composed of synthetic mica and a thin film coating layer, and the thin film coating layer is selected from one of the following: a single layer of "titanium dioxide", two layers of "titanium dioxide / silicon dioxide", and three layers of "titanium dioxide / silicon dioxide / titanium dioxide".

3. The pyrethroid compounds include empenthrin, flamethrin, prallethrin, allethrin, imiprothrin, pyrethrin, phthalthrin, resmethrin, phenothrin, metofluthrin, synerin II, transfluthrin, jasmolin II, cyphenothrin, peratrin, etofenprox, monfluorothrin, permethrin, silafluofen, tefluthrin, and bi A highly light-transmitting insect-repellent and heat-shielding sheet according to claim 1 or 2, wherein the sheet is fentrin and cyfluthrin.

4. The highly light-transmitting insect-repellent and heat-shielding sheet according to any one of claims 1 to 3, wherein the heat-shielding layer contains an ultraviolet-excited keto / enol type tautomer, and the ultraviolet-excited keto / enol type tautomer is one or more selected from benzotriazole compounds, triazine compounds, and diphenyl ketone compounds.

5. The heat shielding layer comprises tungsten oxide, indium oxide, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO), aluminum-doped zinc oxide (AZO), and lanthanum hexaboride (LaB). ６ A highly light-transmitting insect-repellent and heat-shielding sheet according to any one of claims 1 to 4, comprising one or more near-infrared absorbing materials selected from phthalocyanine compounds, naphtholquinone compounds, iminium compounds, anthraquinone compounds, aminium compounds, and nickel-thiol complex compounds, wherein the heat-shielding layer is colored.

6. An antifouling layer is provided on the heat-reflective layer, and within this antifouling layer are tungsten oxide, indium oxide, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO), aluminum-doped zinc oxide (AZO), and lanthanum hexaboride (LaB ６ A highly light-transmitting insect-repellent and heat-shielding sheet according to any one of claims 1 to 4, comprising one or more near-infrared absorbing materials selected from, wherein the anti-fouling layer possesses both anti-fouling and heat-shielding properties.

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