Insect proof partition sheet

Abstract

To provide a partition sheet having an insect proof effect and excellent in transparency (visibility to an opposite side of the sheet), the partition sheet capable of more stably maintaining the insect proof effect than conventional compositions.SOLUTION: A partition sheet is composed of a transparent and flexible laminate, with a soft vinyl chloride resin coating layer formed on a front face and a back face of a lattice-like net. The soft vinyl chloride resin coating layer includes a pyrethroid compound and a cellulose nanofiber. Contents thereof are respectively 1 to 5 mass% (pyrethroid compound) and 0.2 to 2 mass% (cellulose nanofiber), based on the mass of the soft vinyl chloride resin coating layer. Specifically, two types of pyrethroid compound are used, and a difference between molecular masses of both types is 40 to 160. The cellulose nanofiber carries the pyrethroid compound (with the smaller molecular mass).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flexible and see-through (highly visible) partition sheet for use at factory entrances, inside factories, warehouses, offices, conference rooms, medical facilities, government offices, event venues, amusement facilities, campsites, swimming pools, open terraces (dining facilities), horticultural facilities, orchards, shelters, simple rain shelters, food stalls, etc., and particularly to a partition sheet having an insect repellent effect. More specifically, the present invention relates to a partition sheet having an excellent insect repellent effect and a long-lasting effect. [Background technology]

[0002] Flexible partition sheets include laminates with a thickness of 0.25mm to 0.50mm (film part within the grid) made of a polyester grid net as a base material, with transparent soft polyvinyl chloride resin film thermally laminated on both sides, as well as curtain sheets with a thickness of 0.50mm to 2.0mm that do not include a base material. These partition sheets are used in a wide variety of places, such as factory entrances and exits, inside factories, warehouses, offices, conference rooms, clean booths, medical facilities, government offices, event venues, amusement facilities, campsites, pools, open terraces (food and beverage facilities), horticultural facilities, orchards, shelters, house verandas, food stalls, etc.

[0003] In particular, sheet shutters and flexible curtains installed at factory entrances and exits are widely colored in yellow to orange to prevent flies and mosquitoes from entering the factory, and this coloring is a device to absorb and eliminate wavelengths of 400 to 480 nm. Furthermore, an invention has been disclosed for a partition material (Patent Document 1, Patent Document 2) that absorbs and eliminates wavelengths of 380 nm or less when used in combination with an ultraviolet absorber, thereby dulling the sensitivity of insects to light sources such as sunlight and lighting, and providing a blinding effect that keeps phototactic pests away, but this blinding effect is not effective against non-phototactic insects. On the other hand, products that use pyrethroid-based insect repellents that have insecticidal and paralyzing (knockdown) effects as insect repellent (repellent) products against all kinds of insects (insect repellent sheets for chests, insecticidal aerosols, etc.) are commercially available. Products that use pyrethroid-based insect repellents kneaded into resin have a problem of the pyrethroid-based insect repellent bleeding onto the product surface over time. The applicant aimed to provide an industrial material sheet, such as a space partition sheet, that has a stable long-term control effect (repellency) against flying pests, and proposed the use of cyclodextrin-silica composite particles carrying a pyrethroid compound (Patent Document 3). However, this composite carrier had the drawback of impairing the transparency (visibility of the other side) of the partition sheet.

[0004] In addition, an invention (Patent Document 4) has been proposed in which a pyrethroid insect repellent is used in combination with the partition material of Patent Documents 1 and 2 as an insect repellent partition sheet with a smaller amount of pyrethroid insect repellent, and it is described that by changing the average polymerization degree of the vinyl chloride resin, it is possible to control the release of the insect repellent ingredient, and that the higher the average polymerization degree, the longer the insect repellent ingredient will remain in the material, resulting in excellent sustained release of the insect repellent ingredient. However, the extent of this effect and its relationship with the type and amount of plasticizer used have not been clarified. As described above, there is a demand for partition sheets with insect repellent properties that do not impair transparency (visibility behind the sheet) and that have a longer sustained release effect of the insect repellent ingredient, but a partition sheet with such a balance of performance does not exist yet. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 62-278931 [Patent Document 2] JP 2002-114606 A [Patent Document 3] JP 2014-223043 A [Patent Document 4] JP 2020-109070 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a partition sheet that has excellent transparency (visibility on the other side of the sheet) and an insect repellent effect, and that maintains the insect repellent effect more stably than conventional formulations. By solving this problem, the insect repellent effect lasts longer, which not only enables a wide range of applications such as factory entrances and exits, inside factories, warehouses, offices, conference rooms, medical facilities, government offices, event venues, amusement facilities, campsites, pools, open terraces (food and beverage facilities), horticultural facilities, orchards, shelters, simple rain shelters, and food stalls, but also extends the product's life cycle, reducing the waste of resources required for the production of the partition sheet and helping to reduce greenhouse gas emissions. [Means for solving the problem]

[0007] As a result of considering these points and carrying out extensive research, the inventors have discovered that the present invention provides a partition sheet made of a transparent, flexible laminate having a soft polyvinyl chloride resin coating layer on the front and back surfaces of a lattice-like net, wherein the soft polyvinyl chloride resin coating layer contains a pyrethroid compound and cellulose nanofibers, the respective contents of which are 1 to 5 mass % (the pyrethroid compound) and 0.2 to 2 mass % (the cellulose nanofibers) relative to the mass of the soft polyvinyl chloride resin coating layer, thereby resulting in an insect-repellent partition sheet that has excellent transparency (visibility on the other side of the sheet) and an insect-repellent effect that lasts more stably than conventional formulations, and have thus completed the present invention.

[0008] In the insect-repellent partition sheet of the present invention, the pyrethroid compound is preferably empenthrin, furamethrin, prallethrin, allethrin, imiprothrin, pyrethrin, phthalthrin, resmethrin, fenothrin, metofluthrin, cinerin II, transfluthrin, jasmolin II, cyphenothrin, peratrin, etofenprox, momfluorothrin, permethrin, silafluofen, tefluthrin, bifenthrin, and cyfluthrin. By blending such pyrethroid compounds in the partition sheet (blending at 1 to 5% by mass relative to the mass of the soft polyvinyl chloride resin coating layer), an insect-repellent effect (killing, repellency, or knockdown) is obtained.

[0009] The insect-repellent partition sheet of the present invention preferably uses two kinds of pyrethroid compounds in combination, the difference in molecular weight 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 difference in molecular weight to 40 to 160 and further specifying the combined ratio, it is possible to provide an insect repellent effect (killing, or repelling, or knocking down) according to the type of insect, with a time lag effect of immediate action (fast effect) to residual effect (long-lasting effect), making it an all-purpose type.

[0010] In the insect-repellent partition sheet of the present invention, the cellulose nanofibers preferably support the pyrethroid compound. By allowing the cellulose nanofibers to absorb (soak into) the pyrethroid compound (liquid), the cellulose nanofibers are made transparent (their wet state suppresses diffuse reflection and changes the refractive index), and at the same time, the insect-repellent effect can be exerted over a longer period of time by the sustained release effect of the pyrethroid compound while ensuring the transparency of the insect-repellent partition sheet.

[0011] In the insect-repellent partition sheet of the present invention, the cellulose nanofibers preferably support the pyrethroid compound (a pyrethroid compound having a smaller molecular weight), which makes the cellulose nanofibers transparent and ensures the transparency of the insect-repellent partition sheet, while improving the expression of the insect-repellent effect due to the sustained release effect of the pyrethroid compound over a longer period of time and the durability of the fast-acting insect repellent.

[0012] In the insect-repellent partition sheet of the present invention, the soft vinyl chloride resin coating layer preferably contains one or more keto / enol tautomers selected from benzotriazole tautomers, triazine tautomers, and diphenyl ketone tautomers, and the content thereof is 0.2 to 2 mass% relative to the mass of the soft vinyl chloride resin coating layer. By incorporating such a keto / enol tautomer in the partition sheet (0 part by mass or 0.2 to 1.0 part by mass relative to the mass of the soft vinyl chloride resin coating layer), wavelengths shorter than 400 nm are converted into thermal energy, thereby achieving an insect blinding effect.

[0013] In the insect-proof partition sheet of the present invention, the soft vinyl chloride resin coating layer preferably contains a colorant, is yellow to reddish brown, and is transparent, thereby absorbing and eliminating wavelengths of 400 to 480 nm and simultaneously ensuring the transparency of the insect-proof partition sheet. Effect of the Invention

[0014] The present invention makes it possible to provide a partition sheet that has excellent transparency (visibility on the other side of the sheet) and an insect-repellent effect, and whose insect-repellent effect lasts longer than that of conventional formulations.This not only makes it possible for the sheet to be used in a wide range of places, such as factory entrances and exits, inside factories, warehouses, offices, conference rooms, medical facilities, government offices, event venues, amusement facilities, campsites, swimming pools, open terraces (food and beverage facilities), horticultural facilities, orchards, shelters, simple rain shelters, and food stalls, but also extends the product's life cycle, thereby reducing the waste of resources required for the production of the partition sheet and helping to reduce greenhouse gas emissions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The insect-repellent partition sheet of the present invention is a partition sheet made of a transparent and flexible laminate in which a soft vinyl chloride resin coating layer is provided on the front and back surfaces of a lattice-like net, and the soft vinyl chloride resin coating layer contains a pyrethroid compound and cellulose nanofibers, and the respective contents are 1 to 5 mass% (pyrethroid compound) and 0.1 to 1.0 mass% (cellulose nanofibers) relative to the mass of the soft vinyl chloride resin coating layer. Alternatively, the pyrethroid compound is a combination of two pyrethroid compounds with a molecular weight difference of 40 to 160. Alternatively, the cellulose nanofibers support a pyrethroid compound (particularly the pyrethroid compound with a smaller molecular weight). Alternatively, the soft vinyl chloride resin coating layer contains a keto / enol tautomer, and the content thereof is 0.1 to 1.0 mass% relative to the mass of the soft vinyl chloride resin coating layer. Alternatively, the soft vinyl chloride resin coating layer contains a colorant, is yellow to reddish brown, and is transparent.

[0016] The lattice-like net used in the insect-proof partition sheet of the present invention is any one selected from 1) a square lattice net or a biaxially stretched net woven with a warp / multifilament yarn group and a weft / multifilament yarn group, or 2) a triaxial net fabric with a triangular lattice woven with a warp / multifilament yarn group, particularly a 30° left-upward and 30° right-upward bias / multifilament yarn group, or 3) a four-axial net including a square lattice / triangular lattice woven with a warp and weft / multifilament yarn group, particularly a 45° left-upward and 45° right-upward bias / multifilament yarn group, or a net obtained by coating the entirety of any one of the nets 1) to 3) with one selected from vinyl chloride resins, ethylene-vinyl acetate copolymer resins, urethane resins, acrylic resins, and polyvinyl alcohol resins (particularly water-based resins), and 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. Alternatively, 4) a square lattice net obtained by stacking warp / resin-processed multifilament yarns and weft / resin-processed multifilament yarns (non-woven fabrics such as stacking a weft on top of a warp, or a non-woven fabric obtained by sandwiching a weft between two warps) and thermally bonding them, or 5) a triaxial net with a triangular lattice obtained by stacking warp / resin-processed multifilament yarns, particularly 30° left-up and 30° right-up bias / resin-processed multifilament yarns (non-woven fabrics such as stacking a left-up (or right-up) bias yarn on top of a warp, and then stacking a right-up (or left-up) bias yarn on top of that) and thermally bonding them, or 6) a warp and weft / resin-processed multifilament yarn A four-axis net including a square lattice / triangular lattice formed by stacking (such as a non-woven fabric in which a weft thread group is layered on top of a warp thread group, a left-up (or right-up) bias thread group is layered on top of that, and a right-up (or left-up) bias thread group is layered on top of that) and heat-bonding using groups, particularly 45° left-up and 45° right-up bias / resin-processed multifilament yarn groups, and the resin processing of the lattice-shaped net in 4) to 6) is a net coated with one type (particularly a water-based resin) selected from vinyl chloride resin, ethylene-vinyl acetate copolymer resin, urethane resin, acrylic resin, and polyvinyl alcohol resin, and 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.

[0017] The porosity of the lattice nets in 1) to 6) above is 70 to 95%, especially 75 to 90%, and the area per lattice in 1) and 4) is 80 mm 2 ~625mm 2 The yarn spacing is 9mm to 25mm, and the weight is 10 to 75g / m 2 The area of ​​each grid in 2) and 5) is 70 mm 2 ~500mm 2 The range is 9mm to 25mm for the interval between warp and bias yarns, and the mass is 15 to 100g / m 2 In addition, the area of ​​each triangular lattice in 3) and 6) is 50 mm 2 ~200mm 2 Within the range, and the area of ​​each square grid is 100 mm 2 ~1600mm 2 The yarn spacing is 10mm to 40mm, and the mass is 20 to 150g / m 2 It is.

[0018] The multifilament yarn is one or more types of multifilament (100 to 500 single yarns having a diameter of 1 to 20 μm are bundled, and the carbon fiber is 1500 to 3000 single yarns having a diameter of 0.3 to 1.5 μm are bundled) selected from glass fiber, polyester fiber (including the category of wholly aromatic polyester fiber), polyamide fiber (including the category of wholly aromatic polyamide fiber), polypropylene fiber, vinylon fiber, carbon fiber, and aromatic heterocyclic polymer fiber (polybenzoxazole, polybenzimidazole, polybenzothiazole). In particular, the polyester fiber is preferably polyethylene terephthalate, and the polyamide fiber is preferably 6 nylon, 6,6 nylon, 6,10 nylon, etc., which are synthesized from fossil fuel-derived monomers, or synthesized from monomers derived partially or entirely from biomass, or recycled materials, or further preferably decomposed into monomers and repolymerized from recycled polyester. The multifilament yarn is preferably a multifilament yarn having a fineness of 138 to 1111 dtex (decitex) and twisted at a pitch of 0 to 1 turn / 25 mm. Although a non-twisted yarn having a twist number of 0 may be used, a weakly twisted yarn having a twist number of 0.5 to 0.7 turns is particularly preferred for preventing fraying of the yarn and for ease of handling. One to three of these multifilament yarns may be used, and two or three of these may be combined and twisted to form a combined and twisted yarn. These multifilament yarns may be optionally dyed, colored (original dyeing in which a colorant is used in combination with the fiber during fiber production), treated with a sizing agent (starch, polymer), water-repellent (perfluoroalkyl group-containing copolymer resin), flame-retardant (phosphate ester), etc., and it is particularly preferable to modify the glass fiber surface with a known silane coupling agent to improve adhesion to the soft vinyl chloride resin coating layer.

[0019] The thickness of the soft vinyl chloride resin coating layer laminated on the front and back of the lattice net is 0.12 mm to 0.6 mm. If the thickness of the soft vinyl chloride resin coating layer is thinner than 0.12 mm, holes may occur in the part covering the lattice net due to film breakage during hot pressure melt lamination, and if it exceeds 0.6 mm, the partition sheet itself may become heavy and difficult to handle. The soft vinyl chloride resin coating layer is a film (sheet) having a thickness of 0.12 mm to 0.6 mm, which is made by calendar molding or T-die extrusion molding of a soft vinyl chloride resin composition compound. The basic composition of the soft polyvinyl chloride resin composition is a compound containing polyvinyl chloride resin (100 parts by mass), a plasticizer (40 to 60 parts by mass), a stabilizer for polyvinyl chloride resin (1 to 5 parts by mass), a pyrethroid compound (preferably 1.4 to 8.5 parts by mass), and cellulose nanofiber (preferably 0.28 to 3.2 parts by mass), in which the content of the pyrethroid compound relative to the mass of the soft polyvinyl chloride resin coating layer is 1 to 5 mass%, and the content of the cellulose nanofiber is 0.2 to 2 mass%. The vinyl chloride resin is preferably a vinyl chloride resin having a number average molecular weight of 1000 to 2000 (mainly vinyl chloride resin, crosslinked vinyl chloride resin, chlorinated vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, acrylic-(graft)vinyl chloride copolymer, urethane-vinyl chloride (graft) copolymer, etc., preferably a biomass synthesis product thereof), and the plasticizer is preferably an adipic acid ester compound (DOA, DINA, DIDA, etc.), a phthalate ester compound (DOP, DINP, DIDP, DUP, etc.), a cyclohexane dicarboxylate ester compound, a cyclohexene dicarboxylate ester compound, a trimellitic acid tris ester plasticizer, a pyromellitic acid tetrakis ester plasticizer, an aromatic phosphate ester compound (TCP, CDP, TPP, etc.), a chlorinated paraffin compound, a polyester compound, etc., and a biomass synthesis product thereof. In addition, as the stabilizer, a barium-zinc complex, a calcium-zinc complex, an epoxidized soybean oil, etc. are preferable.Furthermore, the soft vinyl chloride resin composition may contain a keto / enol tautomer (preferably 0.28 to 3.2 parts by mass: content of 0.2 to 2% by mass), and may further contain a small amount of a colorant (yellow to reddish brown). The combined use of the keto / enol tautomer and the colorant (yellow to reddish brown) exhibits a cut effect for wavelengths of 480 nm or less. In addition, other additives may be used on the condition that they do not impair the transparency (visibility) of the soft vinyl chloride resin coating layer. Examples of other additives include adhesives (polyfunctional isocyanate compounds, silane coupling agents, etc.), antifungal agents (imidazole compounds, thiazole compounds, isothiazolin compounds, pyridine compounds, N-haloalkylthio compounds, phenoxyarsine compounds, etc.), pigments (azo compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, etc.), fluorescent whitening agents, antistatic agents, surfactants, antioxidants, fragrances, etc.

[0020] The pyrethroid compounds contained in the soft polyvinyl chloride resin coating layer 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-cyclopropanecarboxylate), furametrin (also known as vinamine 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 Etoc: C 19 H 24 O3: molecular weight 300.4 (chemical name: (+)-2-methyl-4-oxo-3-(2-propynyl)(±)-2-cyclopentenyl (+)-cis / trans chrysanthemate), allethrin (also known as pynamine: C 19 H 26 O3: molecular weight 302.4 (chemical name: Dl-3-allyl-2-methylcyclopent-2-en-4-one-1-yl-DL-cis, trans chrysanthemate), imiprothrin (also known as Pral: C 17 H 22N2O4: molecular weight 318.3 (chemical name: 2,5-dioxo-3-prop-2-ynyl imidazolidin-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: mixture of pyrethrin I, II, cinerin I, II, and jasmolin I, II) Phthalthrin (also known as neopynamin: C 19 H 25 NO4: molecular weight 331.4 (chemical name: N-(3,4,5,6-tetrahydrophthalimido)methyl-D,L-cis,trans chrysanthemate), resmethrin (also known as Chryslon: C 22 H 26 O3: molecular weight 338.5 (chemical name: (5-benzyl-3-furyl)methyl d-cis, trans chrysanthemate), fenothrin (also known as sumithrin: 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), Cinerin 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 Gokirate: C 24 H 25 NO3: molecular weight 375.5 (chemical name: cyano(3-phenoxyphenyl)methyl = 2,2-dimethyl-3-(2-methylprop-1-en-1-yl) cyclopropanecarboxylate), peratorin (C 18 H 21 ClO4: molecular weight 375.5), etofenprox (C 25 H28 O3: molecular weight 376.5 (chemical name: 2-(4-ethoxyphenyl)-2-methylpropyl = 3-phenoxybenzyl ether) (no chrysanthemum acid structure), Momfluorotrin (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 22 ClF3O2: 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 Baythroid: C 22 H 18 Cl2FNO3: molecular weight 434.3 (chemical name: α-cyano(4-fluoro-3-phenoxy)benzyl = 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylate) ... (The most of these pyrethroid compounds have a chrysanthemum acid structure in their molecular structure, which acts as an insect repellent (killing, repellent, knockdown) effect).

[0021] The combined use of two pyrethroid compounds is carried out in a combined mass ratio of 1:3 to 3:1, with a molecular weight difference of 40 to 160, particularly 60 to 140, with 1.3 to 8.5 parts by mass relative to 100 parts by mass of vinyl chloride resin, and 1 to 5% by mass, preferably 3 to 5% by mass, relative to the soft vinyl chloride resin coating layer. If the blending amount is less than this, the long-term insect repellent effect cannot be achieved, and if the blending amount is greater than this, the surface of the partition sheet becomes sticky due to bleeding (oozing) of the pyrethroid compound. By using two types of compounds that satisfy this blending condition, it is possible to provide a time-lag effect of immediate action (fast effect) to residual effect (sustained effect) in the insect repellent effect (insect killing, repellency, or knockdown). When two pyrethroid compounds are used in combination, the difference in molecular weight between the two is 40-160, and the mass ratio of the pyrethroid compound with the smaller molecular weight to the pyrethroid compound with the larger molecular weight is 3:1 or close to this (approximately 3:1-5:3), the formulation will be mainly immediate-acting and yet have excellent residual effects. On the other hand, when the mass ratio of the pyrethroid compound with the smaller molecular weight to the pyrethroid compound with the larger molecular weight is 1:3 or close to this (approximately 1:3-3:5), the formulation will be mainly residual-acting and yet have excellent immediate-acting effects. When the molecular weight difference is less than 40, the difference between immediate-acting and residual effects may be unclear. The effect of using two pyrethroid compounds in combination is particularly noticeable in soft polyvinyl chloride resins containing 20-40% by mass of plasticizer (molecular weight 370-475). As synergists that enhance the action of pyrethroid compounds, 5-[2-(2-butoxyethoxy)]-6-propyl-1,3-benzodioxole, N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dicarboximide, octachlorodipropyl ether, etc. can be used in amounts 1 to 10 times the amount of the pyrethroid compound (total). These act as inhibitors of the microsomal complex oxidase enzymes that metabolize and decompose insecticides in the insect's body, thereby suppressing the decomposition of pyrethroid compounds in the insect's body and thereby enhancing the efficacy of the insecticide.Other insect repellent ingredients include the following common names: dichlorvos, pyridaphenthion, fenitrothion, depending on the type of pest (mosquitoes, flies, termites, cockroaches). Fenthion, phoxim, diazinon, propetamphos, tetrachlorvinphos, fenobucarb, carbaryl, propoxur, troysan, DEET, icaridin, pyriproxyfen, methoxadiazone, fipronil, hydramethylnon, amidoflumet, clothianidin, acetamiprid, imidacloprid, thiamethoxam, silafluofen, chlorfenapyr, etc., which can be used in combination with the pyrethroid compound in the same amount or less.

[0022] The cellulose nanofibers contained in the soft polyvinyl chloride resin coating layer can be either unmodified cellulose nanofibers obtained by mechanical treatment or modified cellulose nanofibers obtained by chemical treatment, and the amount of these is preferably 0.24 to 3.2 parts by mass relative to 100 parts by mass of polyvinyl chloride resin, and 0.2 to 2% by mass, preferably 0.75 to 2% by mass, relative to the soft polyvinyl chloride resin coating layer. If the amount is less than this, the amount of pyrethroid compound supported is insufficient and long-term insect repellent effect cannot be achieved, and if the amount is more than this, the transparency of the partition sheet (visibility behind the sheet) tends to be hindered. Modified cellulose nanofibers include carboxymethylated cellulose, oxidized cellulose, borate esterified cellulose, phosphate esterified cellulose, silicate esterified cellulose, isocyanated cellulose, aminosilane-modified cellulose, vinylsilane-modified cellulose, epoxysilane-modified cellulose, methacrylsilane-modified cellulose, acrylicsilane-modified cellulose, chlorosilane-modified cellulose, mercaptosilane-modified cellulose, isocyanurate silane-modified cellulose, isocyanate silane-modified cellulose, etc. By carrying (absorb-ing) a pyrethroid compound (liquid) on these cellulose nanofibers, the cellulose nanofibers are made transparent (in a wet state, diffuse reflection is suppressed and the refractive index is changed), and at the same time, the performance of controlling the sustained release of the pyrethroid compound is imparted while ensuring the transparency of the insect-repellent partition sheet. The amount of pyrethroid compound supported on the cellulose nanofiber does not need to be the total amount of pyrethroid compound formulated; approximately 10 to 50 mass% of the pyrethroid compound is necessary and sufficient. The mixture of free pyrethroid compound (immediate sustained release) and cellulose nanofiber-supported pyrethroid compound (long-term sustained release) ensures a stable insect repellent effect from the start of use.In particular, the use of two pyrethroid compounds in combination is preferred, with a molecular weight difference between the two being 40-160, and a mass ratio of the pyrethroid compound with the smaller molecular weight to the pyrethroid compound with the larger molecular weight being 1:3-3:1. The pyrethroid compound supported on the cellulose nanofiber is the pyrethroid compound with the smaller molecular weight (not necessarily the entire amount, about 10-50 mass% is sufficient), which provides a more stable and sustained insect repellent effect. Cellulose nanofibers are short fibers (powder, slurry, dispersion liquid form) made by mechanically defibrating (roughly defibrating or finely defibrating) cellulose raw materials (chemically treated pulp, mechanically crushed pulp, waste paper pulp, etc.) to nanosize the fiber diameter, with an average aspect ratio (average fiber length / average fiber diameter) of 10-50, an average fiber diameter of 3nm-100nm, and an average fiber length of 100μm or less, especially 300nm-500nm, and consisting of a crystalline part, a quasi-crystalline part, and an amorphous part.

[0023] The modified cellulose nanofibers can be carboxymethylated, oxidized, esterified (one or more selected from borate esterification, phosphoric acid esterification, and silicate esterification), isocyanated, or treated with a silane coupling agent (aminosilane-modified, vinylsilane-modified, epoxysilane-modified, methacrylsilane-modified, acrylsilane-modified, chlorosilane-modified, mercaptosilane-modified, isocyanurate silane-modified, or isocyanate silane-modified). In particular, carboxymethylation is performed by carboxymethylating the primary and secondary hydroxyl groups (2,3,6 positions) of cellulose, and oxidation modification is performed by selectively converting only the primary hydroxyl groups (C6-OH groups) of the cellulose of the pulp to C6-carboxyl group Na salts using an oxidation catalyst solution containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical) catalyst, NaBr, and sodium hypochlorite, resulting in a COOH group amount of 0.8 to 1.7 mmol / g. In addition, silane coupling agent treatment (amino silane modification, vinyl silane modification, epoxy silane modification, methacryl silane modification, acrylic silane modification, chloro silane modification, mercapto silane modification, isocyanurate silane modification, isocyanate silane modification, etc.) is carried out by treating cellulose nanofibers with an aqueous solution containing one or more silane coupling agents, and the hydrolyzate of the silane coupling agent: XR-Si(OH)3 (X = amino group, vinyl group, epoxy group, methacryl group, acrylic group, chloro group, mercapto group, isocyanurate group, isocyanate group, etc. (R = alkyl chain) is added to the cellulose. It is one or more reaction products bonded to hydroxyl groups, carboxyl groups, etc. of cellulose nanofibers. In the present invention, non-modified cellulose nanofibers or modified cellulose nanofibers (particularly modified ones treated with a silane coupling agent) are used, and a pyrethroid compound is supported on these, thereby imparting the effect of controlled sustained release of the pyrethroid compound. When a pyrethroid compound is supported on these, it has excellent affinity with the modified cellulose nanofibers, and this affinity makes it possible to impart the effect of stably controlling the sustained release of the pyrethroid compound.

[0024] Examples of the silane coupling agent include one or more selected from aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylicsilane, chlorosilane, mercaptosilane, isocyanurate silane, and isocyanate silane. The silane coupling agent is an alkoxysilane compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si(Y)3, for example, X=amino group, vinyl group, epoxy group, methacryl group, acrylic group, chloro group, mercapto group, isocyanurate group, isocyanate group, etc. (R=alkyl chain), Y=methoxy group, ethoxy group, etc. The silane coupling agent is hydrolyzed in an aqueous solution to produce the general formula: XR-Si(OH)3, and this hydrolyzate bonds with the primary and secondary hydroxyl groups (2, 3, and 6 positions) and carboxyl groups of the cellulose molecule to obtain cellulose nanofibers treated with a silane coupling agent. In particular, a silane coupling agent in which X=amino group, epoxy group, mercapto group, isocyanate group, or the like is suitable for such bonding.

[0025] As for modification by esterification, boric acid esterification is a modification in which cellulose nanofibers are treated with boric acid such as orthoboric acid (H3BO3) or metaboric acid (HBO2) or borate aqueous solutions such as sodium tetraborate hydrate (Na2B4O7·10H2O) or sodium pentaborate (NaB5O8), and the boric acid components react with the hydroxyl and carboxyl groups of the cellulose nanofibers. Phosphate esterification is a modification in which nanocellulose is treated with orthophosphoric acid (H3PO4), pyrophosphoric acid, polyphosphoric acid (HPO3)n In this modification, the cellulose nanofibers are treated with an aqueous solution of phosphoric acid, such as phosphorous acid or phosphinous acid, or a phosphate salt, such as a metal salt or ammonium salt derived from these phosphoric acids, to react with the phosphoric acid component on the hydroxyl and carboxyl groups, etc. of the cellulose nanofibers, while in the case of silicic acid esterification, the cellulose nanofibers are treated with an aqueous solution of silicic acid or a silicate salt, such as sodium silicate (water glass), lithium silicate, or potassium silicate, to react with the hydroxyl and carboxyl groups, etc. of the cellulose nanofibers. When a pyrethroid compound is supported on these, it has excellent affinity with the modified cellulose nanofibers, and this affinity can impart the effect of stably controlling the sustained release of the pyrethroid compound.

[0026] The keto / enol tautomer contained in the soft vinyl chloride resin coating layer is one or more selected from benzotriazole tautomers, triazine tautomers, and diphenyl ketone tautomers, and a mixture of these three types (for example, a mass ratio of 1:1:1 or close thereto) is particularly preferred. Keto / enol tautomers are organic compounds that can be reversibly converted between R2-CH-(C=O)-R1 (keto isomer) and R2-C=CH(OH)-R1 (enol isomer), and have the property that both isomers, keto type and enol type, repeatedly convert to each other and coexist in equilibrium. These include benzotriazole compounds having a molecular weight in the range of 250 to 700, particularly enol types such as hydroxyphenylbenzotriazole derivatives, and benzotriazole derivatives having a molecular weight of 250 to 700. Triazine compounds having a molecular weight in the range of 0 to 700, particularly as an enol type, hydroxyphenyl-1,3,5-triazine derivatives, and diphenyl ketone compounds having a molecular weight in the range of 200 to 400, particularly as an enol type, hydroxydiphenyl ketone derivatives are preferred, and the blending amount of these is preferably 0.24 to 3.2 parts by mass relative to 100 parts by mass of vinyl chloride resin, and 0.2 to 2 mass% and preferably 0.75 to 2 mass% relative to the soft vinyl chloride resin coating layer. If the blending amount is less than this, the ultraviolet ray removal effect becomes poor and the insect repellent effect cannot be expressed, and even if the blending amount is more than this, there is a tendency that a corresponding ultraviolet ray removal effect cannot be obtained. By including keto / enol tautomers in the soft polyvinyl chloride resin coating layer, the keto / enol tautomers are excited by ultraviolet light emitted from a light source or sunlight, and the keto / enol tautomers repeatedly convert between the enol isomer and the keto isomer in nanoseconds. This converts ultraviolet energy into molecular vibration energy for the conversion and releases it outside the system, resulting in an ultraviolet elimination effect that reduces the amount of wavelengths of 380 nm or less that penetrate the insect-repellent partition sheet, and as insects cannot sense wavelengths of 380 nm or less, they are prevented from attracting flying insects. Before LED lighting, incandescent bulbs and halogen lamps that emit ultraviolet light that attracts insects were mainstream, but with the recent shift to LED bulbs and LED fluorescent lights that do not emit ultraviolet light or heat, insect attraction caused directly by the light source has become less severe than before.

[0027] The soft vinyl chloride resin coating layer preferably contains a small amount of colorant, is yellow to reddish brown, and has transparency (visibility). Examples of yellow pigments include monoazo yellow, disazo yellow, condensed azo yellow, nickel azo yellow, isoindoline yellow, isoindolinone yellow, naphthol yellow, and quinophthalone yellow, which can be used alone or in combination to produce yellow to orange colors, or orange to reddish brown colors obtained by using these yellow pigments in combination with red pigments. Examples of red pigments include azo lake red, monoazo red (Ca-based or Ba-based), condensed azo red, (dimethyl)quinacridone red, diketopyrrolopyrrole red, thioindigomagenta, perylene red, perinone red, anthraquinonyl red, and quinacridone violet. The partition sheet is made by laminating two films (sheets) with a thickness of 0.12mm to 0.6mm on both sides of a lattice net by thermal fusion, with the front and back soft polyvinyl chloride resin coating layers, so that the other side of the sheet can be seen through the gaps in the lattice net. Therefore, the amount of colorant blended is carried out within a range that does not impair visibility, and for example, the thinnest lattice of 0.12mm x 2 sheets of 0.24mm may be colored with a relatively high concentration, but the thickest lattice of 0.6mm x 2 sheets of 1.2mm must be colored with a low concentration (theoretically 1 / 5 the amount of colorant used in a 0.12mm film) to maintain visibility. This coloring has the effect of making the partition sheet less transparent to wavelengths of 400 to 480nm, making it difficult for insects to detect it. In addition, the combined use of this coloring and the keto / enol tautomer reduces the wavelengths of 480 nm or less that penetrate the insect-repellent partition sheet, making it difficult for insects to detect wavelengths of 480 nm or less, thereby preventing the attraction of flying insects, etc. This blocking effect is maintained even when no pyrethroid compound remains in the soft polyvinyl chloride resin coating layer.

[0028] The soft vinyl chloride resin coating layers on the front and back of the insect-repellent partition sheet of the present invention are made by forming a film (sheet) having a thickness of 0.12 mm to 0.6 mm by calendar molding or T-die extrusion molding of a soft vinyl chloride resin composition compound. The lamination of the soft vinyl chloride resin coating layers on the front and back of the lattice-shaped net can be performed by a method of hot melt pressing using a laminator having 1 to 2 continuous pressing units of a heat roll / rubber roll, a cooling roll unit, and a winding unit, and a process of passing the laminator once or twice. An antifouling coating film layer may be formed on the soft vinyl chloride resin coating layer on the front side of the insect-repellent partition sheet of the present invention. By forming the antifouling layer, the sustained release of the pyrethroid compound is only on the back side of the insect-repellent partition sheet, and the insecticidal effect and knockdown effect are mainly expressed on the back side, but the effect of preventing the arrival of flying insects and the like by the combined use of coloring and keto / enol tautomers is not affected. The antifouling layer can be provided, for example, by a method of applying and drying a paint made of acrylic resin, fluorine-based copolymer resin, acrylic-silicone copolymer resin, acrylic-fluorine copolymer resin, acrylic-urethane copolymer resin, or a blend of acrylic resin and fluorine-based copolymer resin by gravure coating, or by laminating a multilayer film such as a fluorine-containing resin film or a fluorine-containing resin / acrylic resin layer with an adhesive or by thermal melting. Furthermore, a photocatalytic layer containing a photocatalytic inorganic material (for example, photocatalytic titanium oxide, photocatalytic tungsten oxide, etc.) can also be provided on these antifouling layers.

[0029] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following examples and comparative examples, the repellent effect of the partition sheet against flying pests was measured and evaluated by the following test method. 1) Repellent effect against flying pests (KT50) Test 1-1 A 6cm x 6cm square piece of partition sheet was placed in a glass petri dish with a diameter of 8.5cm and a height of 2.5cm, and with the lid on, it was left to acclimate to an environment of 30°C for 30 minutes. Ten adult chironomids (chironomids) were released into the petri dish, and from this point on, the number of chironomids knocked down was counted. The time (seconds) until the number of chironomids knocked down reached half, the fifth, was calculated as the "KT50 value," and it was determined that the smaller this value (average of three tests) was, the higher the insect repellent effect = evasion effect. *KT50 = Median knock-down time (the time required for 50% of test insects to become depressed (unable to get up regardless of whether they are dead or alive)) Test 1-2 The partition sheet pieces after the above test 1 were left in a gear oven at 50°C for 100 days, 125 days, and 150 days. Using these partition sheet pieces, the same test as test 1 was conducted again to determine the "KT50 value" of the repellent effect against midges. It was determined that the smaller this value (average value of three tests) was, the higher the insect repellent effect was. 2) Repellent effect against clothing pests (KT50) Test 2 Ten adult chironomids (mosquitoes) were released into a 30cm (width) x 30cm (depth) x 30cm (height) box (one side without acrylic panel) made of transparent acrylic board, and a 30cm x 30cm piece of partition sheet was attached to seal the box. The box was placed in a dark room with the side with the partition sheet facing the back depth, and a 60W incandescent light bulb installed 50cm behind the side with the partition sheet was turned on for 30 seconds, turning the partition sheet into a lantern-like shape, and the number of chironomids that had gathered on the surface of the partition sheet was counted.

[0030] [Example 1] <Grid net (1)> The warp and weft yarns were made of 1000 denier (1111 dtex) polyethylene terephthalate (PET) multifilament yarns (192 filaments) that had been impregnated with an acrylic resin emulsion to produce a non-twisted yarn (1.2 mm wide). The weft yarns were arranged at 2 cm intervals, and a warp yarn group was arranged on top of them at 2 cm intervals. The intersections of the yarns were fused and fixed by a heat press, and the warp and weft yarns were flattened to a width of 1.2 mm to produce a square lattice net (10 g / m2) made of non-woven fabric with a density of 1.27 yarns / inch and a void ratio of 88%. 2 ) was used. <Partition sheet> This square lattice net was used as a substrate, and a 0.15 mm-thick calendar-molded film made of the soft vinyl chloride resin composition shown in [Formulation 1] below was applied to both sides of the substrate as a soft vinyl chloride resin coating layer on the front and back, and melt-laminated by thermocompression bonding with a laminator to obtain a film with a thickness of 0.3 mm and a mass of 400 g / m. 2 Thus, a transparent partition sheet (1) was obtained. [Formulation 1]: Soft polyvinyl chloride resin composition (compound) Vinyl chloride resin (degree of polymerization 1300) 100 parts by weight Diisononyl phthalate (plasticizer: DINP) 22 parts by weight Diphenylcresyl phosphate (flame retardant plasticizer: CDP) 20 parts by weight Epoxidized soybean oil (plasticizer and stabilizer) 3 parts by weight Barium / zinc composite stabilizer 2 parts by weight Permethrin (pyrethroid compound: Mw391.3) 5 parts by mass Boric acid ester modified cellulose nanofiber (powder) 1.5 parts by mass *3 A solution of boric acid (mass%) + ethyl cellosolve (mass%) was added to the carboxymethylation cell. Cellulose nanofiber (cellulose primary and secondary hydroxyl groups (2, 3, 6 positions) are carboxylated Modified fiber reacted with the carboxymethyl group of methylated fiber: Fiber width 3-10 nm: Fiber length 30~100μm *Borate ester modified cellulose nanofiber (powder) is diisononyl phthalate (Plasticizer: DINP)

[0031] [Example 2] The same as in Example 1 except that [Mixture 1] in Example 1 was changed to [Mixture 2], the thickness was 0.3 mm, and the mass was 400 g / m 2 Thus, a transparent partition sheet (2) was obtained. [Mixture 2] has the same composition as [Mixture 1], except that the pyrethroid compound (permethrin) in [Mixture 1] was changed to 4 parts by mass, and 1.5 parts by mass of borate-esterified modified cellulose nanofiber (powder) was changed to 2.5 parts by mass of borate-esterified modified cellulose nanofiber (exhaustion powder) carrying 1 part by mass of permethrin. Permethrin was carried by blending borate-esterified modified cellulose nanofiber powder with permethrin (liquid) and exhausting it at room temperature and normal pressure for 24 hours, and 100 g of permethrin carrying body was prepared, from which 2.5 parts by mass was used.

[0032] [Example 3] The same as in Example 1 except that [Mixture 1] in Example 1 was changed to [Mixture 3], the thickness was 0.3 mm, and the mass was 400 g / m 2 Thus, a transparent partition sheet (3) was obtained. [Formula 3] has the same composition as [Formula 1], except that the pyrethroid compound (permethrin) in [Formula 1] is changed to 2.5 parts by mass, and 2.5 parts by mass of a new pyrethroid compound (fenothrin: Mw 350.4) is added, resulting in a 1:1 mass ratio combination of two pyrethroid compounds (molecular weight difference 41).

[0033] [Example 4] The same as in Example 1 except that [Blend 3] in Example 3 was changed to [Blend 4], the thickness was 0.3 mm, and the mass was 400 g / m 2 Thus, a transparent partition sheet (4) was obtained. [Blend 4] has the same composition as [Blend 3], except that the pyrethroid compound (fenothrin) in [Blend 3] was changed to 1.5 parts by mass, and the 1.5 parts by mass of borate-esterified modified cellulose nanofiber (powder) was changed to 2.5 parts by mass of borate-esterified modified cellulose nanofiber (exhaustion powder) carrying 1 part by mass of fenothrin (Mw350.4). Fenothrin was carried by blending borate-esterified modified cellulose nanofiber powder with fenothrin (liquid) and exhausting it at room temperature and normal pressure for 24 hours, and 100 g of the fenothrin carrier was prepared, from which 2.5 parts by mass were used.

[0034] [Example 5] 〈Grid net (2)〉 A non-twisted yarn (1.2 mm wide) made of 1000 denier (1111 dtex) polyethylene terephthalate (PET) multifilament yarn (192 filaments) impregnated with an acrylic resin emulsion was used for the warp yarn group and bias yarn group. A 30° right-up bias yarn group was arranged at 2 cm intervals, a warp yarn group was arranged at 2 cm intervals on top of that, and a 30° left-up bias yarn group was arranged at 2 cm intervals on top of that, and the intersections of the yarns were fused and fixed by a heat press to produce a non-woven equilateral triangular lattice net (15 g / m) with a density of 1.27 yarns / inch and a void ratio of 82%, which was flattened to a width of 1.2 mm. 2 ) was used. <Partition sheet> This equilateral triangular lattice net was used as a substrate, and a 0.15 mm-thick calendar-molded film made of the soft vinyl chloride resin composition shown in [Formulation 5] below was applied to both sides of the substrate as a soft vinyl chloride resin coating layer on the front and back, and melt-laminated by thermocompression bonding with a laminator to obtain a film with a thickness of 0.3 mm and a mass of 405 g / m. 2 Thus, a transparent partition sheet (5) was obtained. [Formulation 5]: Soft polyvinyl chloride resin composition (compound) Vinyl chloride resin (degree of polymerization 1300) 100 parts by weight Diisononyl phthalate (plasticizer: DINP) 22 parts by weight Diphenylcresyl phosphate (flame retardant plasticizer: CDP) 20 parts by weight Epoxidized soybean oil (plasticizer and stabilizer) 3 parts by weight Barium / zinc composite stabilizer 2 parts by weight Allethrin (pyrethroid compound: Mw302.4) 5 parts by mass Oxidized cellulose nanofiber (powder) 1.5 parts by mass *Oxidation is TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical) The cellulose in the pulp is oxidized by the catalyst, NaBr, and sodium hypochlorite. Selectively convert only primary hydroxyl groups (C6-OH groups) to C6-carboxyl groups Na salts to COO H group amount 0.8-1.7mmol / g Fiber width 3-10nm: Fiber length 30-100μm *Oxidized cellulose nanofiber (powder) is made using diisononyl phthalate (plasticizer: DI Dispersed in NP) for use

[0035] [Example 6] The thickness was 0.3 mm and the mass was 405 g / m. 2 Thus, a transparent partition sheet (6) was obtained. [Blend 6] has the same composition as [Blend 5], except that the pyrethroid compound (allethrin) in [Blend 5] is changed to 4 parts by mass, and the 1.5 parts by mass of oxidized modified cellulose nanofiber (powder) is changed to 2.5 parts by mass of oxidized modified cellulose nanofiber (exhaustion powder) carrying 1 part by mass of allethrin. The allethrin was carried by blending the oxidized modified cellulose nanofiber powder with allethrin (liquid) and exhausting it at room temperature and normal pressure for 24 hours, and 100 g of the allethrin carrier was prepared, from which 2.5 parts by mass were used.

[0036] [Example 7] The same as in Example 5 except that [Blend 5] in Example 5 was changed to [Blend 7], the thickness was 0.3 mm, and the mass was 405 g / m 2 Thus, a transparent partition sheet (7) was obtained. [Formula 7] has the same composition as [Formula 5], except that the pyrethroid compound (allethrin) in [Formula 5] is changed to 2.5 parts by mass, and 2.5 parts by mass of a new pyrethroid compound (cyfluthrin: Mw 434.3) is added to use two types of pyrethroid compounds in a 1:1 mass ratio (molecular weight difference 132).

[0037] [Example 8] The same as in Example 5 except that [Mixture 7] in Example 7 was changed to [Mixture 8], the thickness was 0.3 mm, and the mass was 405 g / m 2 Thus, a transparent partition sheet (8) was obtained. [Blend 8] has the same composition as [Blend 7], except that the pyrethroid compound (allethrin) in [Blend 7] is changed to 1.5 parts by mass, and the 1.5 parts by mass of oxidized modified cellulose nanofiber (powder) is changed to 2.5 parts by mass of oxidized modified cellulose nanofiber (exhaustion powder) carrying 1 part by mass of allethrin (Mw302.4). The allethrin was carried by blending oxidized modified cellulose nanofiber powder with allethrin (liquid) and exhausting it at room temperature and normal pressure for 24 hours, and 100 g of the allethrin carrier was prepared, from which 2.5 parts by mass were used.

[0038] [Examples 9 to 18] Three types of keto / enol tautomers, namely, a benzotriazole tautomer (0.8 parts by mass), a triazine tautomer (0.8 parts by mass), and a diphenyl ketone tautomer (0.8 parts by mass), were added to [Blend 1] to [Blend 8], and chromophtal azo yellow GR (CI Pigment Y-95) (0.3 parts by mass) and quinacridone red (CI Pigment R207) (0.1 parts by mass) were further added as colorants to form an orange-colored transparent film with a thickness of 0.15 mm. The film was then laminated in the same manner as in Examples 1 to 8 to obtain orange-colored transparent partition sheets (9 to 18). * Benzotriazole tautomers The enol type is an organic compound with MW267, which is a C-N bond between the 1st C of one benzene ring (tert-butyl group at 5 position) with 2-hydroxyl group (1 group) / ketone group (0 groups) and a benzotriazole ring (no substituents). The keto type is an organic compound with MW267, which is a C-N bond between the 1st C of one benzene ring (tert-butyl group at 5 position) with hydroxyl group (0 groups) / ketone group (1 group) with 2-ketone group (0 groups) and a benzotriazole ring (no substituents). The 1st, 2nd, and 5th positions represent the carbon positions of the benzene ring. *Triazine tautomers The enol type is an organic compound with MW367, which is a C-C bond formed by the C-1 positions of three benzene rings (butoxy group at 4 position) with 1 hydroxyl group at 2 position / 0 ketone group at 2 position and the C-C-1 positions of 2, 4, and 6 of the 1,3,5-triazine ring. The keto type is a C-C bond formed by the C-1 positions of three benzene rings (butoxy group at 4 position) with 0 hydroxyl group / 1 ketone group at 2 position and the C-C-1 positions of 2, 4, and 6 of the 1,3,5-triazine ring (MW367), where the 1st, 2nd, and 4th positions represent the carbon positions of the benzene ring, the 2nd, 4th, and 6th C of the triazine ring represent the carbon positions, and the 1st, 3rd, and 5th positions represent the nitrogen N positions. *Diphenyl ketone tautomers The enol type is an organic compound with MW296 in which the 1st C of one benzene ring (no other substituents) with 2-hydroxyl group (1), 2-ketone group (0), and 4-octoxy group (1) is bonded to the benzene ring (no other substituents) via a C=O, and the keto type is an organic compound with MW296 in which the 1st C of one benzene ring (no other substituents) with hydroxyl group (0), 2-ketone group (1), and 4-octoxy group (1) is bonded to the benzene ring (no other substituents) via a C=O, and the 1st, 2nd, and 4th positions represent the carbon positions of the benzene ring.

[0039] [Table 1]

[0040] [Table 2]

[0041] [Table 3]

[0042] Examples 1 and 5 are systems in which the permethrin compound and cellulose nanofibers simply coexist, Examples 2 and 6 are systems in which the permethrin compound and cellulose nanofibers carrying the permethrin compound coexist, Examples 3 and 7 are systems in which two types of permethrin compounds (molecular weight difference 41, 132) simply coexist with cellulose nanofibers, and Examples 4 and 8 are systems in which two types of permethrin compounds (molecular weight difference 41, 132) and cellulose nanofibers carrying the permethrin compound (lower molecular weight side) coexist. It is clear that Examples 2, 4, 6, and 8 in which a part of the permethrin compound is carried on the cellulose nanofibers have a superior durability of insect repellent effect (shorter KT50 seconds at 150 hr) than Examples 1, 3, 5, and 7 in which the permethrin compound and cellulose nanofibers simply coexist. In addition, it is clear that Examples 3 and 7, which use two types of permethrin compounds with different molecular weights in combination, have a longer lasting insect repellent effect (shorter KT50 seconds at 150 hr) than Examples 1 and 5, which use one type of permethrin compound, and that Examples 4 and 8, in which a part of the permethrin compound is supported on cellulose nanofibers, also have a longer lasting insect repellent effect (shorter KT50 seconds at 150 hr) than Examples 2 and 6, which use one type of permethrin compound. In particular, in the insect repellent partition sheets of Examples 9 to 16, in which the soft vinyl chloride resin coating layer of the insect repellent partition sheets of Examples 1 to 8 contains a keto / enol tautomer and further contains a colorant to be yellow to reddish brown and transparent, it is clear that a blinding effect against phototactic insects can be obtained by eliminating wavelengths shorter than 480 nm.In contrast, the insect repellent sheets of Examples 1 to 8 have the ability to attract phototactic insects, but in this day and age, the incandescent light bulbs (which emit wavelengths that attract insects) used in Test 2 are no longer in use and have been replaced by energy-saving LED lamps (which do not emit wavelengths that attract insects), making it unnecessary to take measures against phototactic insects as a light source. Therefore, it is not necessary to specifically include a keto / enol tautomer and further include a colorant to make the sheet yellow to reddish brown and transparent, but as a measure against the wavelengths contained in sunlight that attract insects, the inclusion of a keto / enol tautomer in particular has the effect of converting ultraviolet rays, which is the action of the keto / enol tautomer, into thermal energy and releasing it outside the system, which is meaningful for outdoor use.

[0043] [Comparative Example 1] The same as in Example 1 except that 1.5 parts by mass of borate esterified modified cellulose nanofiber was omitted from [Composition 1] in Example 1, and the thickness was 0.3 mm and the mass was 400 g / m 2 A transparent partition sheet (17) was obtained. By omitting the cellulose nanofiber, the duration of the effect of the pyrethroid compound was shortened. In other words, it is clear from the comparative example that the presence of cellulose nanofiber extends the insect repellent effect of the conventional insect repellent formulation.

[0044] [Comparative Example 2] The same procedure as in Example 3 was repeated except that 1.5 parts by mass of borate esterified modified cellulose nanofiber was omitted from [Blend 3] in Example 3. The thickness was 0.3 mm and the mass was 400 g / m. 2 A transparent partition sheet (18) was obtained. Because the cellulose nanofibers were omitted, the duration of the effect of the pyrethroid compound was short. In other words, it is clear from the comparative example that the presence of cellulose nanofibers extends the insect repellent effect of the conventional insect repellent formulation.

[0045] [Comparative Example 3] The same procedure as in Example 1 was repeated except that 1.5 parts by mass of borate esterified cellulose nanofiber was omitted 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 size of 1.4 μm) from [Composition 1] in Example 1, and the thickness was 0.3 mm and the mass was 405 g / m. 2 The obtained partition sheet (19) had poor visibility due to the replacement of cellulose nanofibers with silica, and the long-term sustained release effect of the pyrethroid compound was lost.

[0046] [Comparative Example 4] The same procedure as in Example 1 was repeated except that 1.5 parts by mass of boric acid esterified modified cellulose nanofiber was omitted and replaced with 1.5 parts by mass of β-cyclodextone (number of glucose molecules: 7, molecular weight: 1135, cavity inner diameter: 0.7-0.8 nm, cavity depth: 0.7-0.8 nm). The thickness was 0.3 mm and the mass was 405 g / m. 2 The obtained partition sheet (20) was clouded and had lost visibility due to the effect of replacing the cellulose nanofibers with silica.

[0047] [Table 4] [Industrial Applicability]

[0048] The present invention makes it possible to provide a partition sheet that has excellent transparency (visibility on the other side of the sheet) and an insect-repellent effect, and whose insect-repellent effect lasts longer than that of conventional formulations.This not only makes it possible for the sheet to be used in a wide range of places, such as factory entrances and exits, inside factories, warehouses, offices, conference rooms, medical facilities, government offices, event venues, amusement facilities, campsites, swimming pools, open terraces (food and beverage facilities), horticultural facilities, orchards, shelters, simple rain shelters, and food stalls, but also extends the product's life cycle, thereby reducing the waste of resources required for the production of the partition sheet and helping to reduce greenhouse gas emissions.

Claims

1. The present invention provides an insect-repellent partition sheet comprising a transparent and flexible laminate having a lattice-like net with soft polyvinyl chloride resin coating layers on the front and back surfaces thereof, the soft polyvinyl chloride resin coating layer containing a pyrethroid compound and cellulose nanofibers, the respective contents of which are 1 to 5 mass% (the pyrethroid compound) and 0.2 to 2 mass% (the cellulose nanofibers) relative to the mass of the soft polyvinyl chloride resin coating layer.

2. The insect-repellent partition sheet according to claim 1, wherein the pyrethroid compound is empenthrin, furamethrin, prallethrin, allethrin, imiprothrin, pyrethrin, phthalthrin, resmethrin, fenothrin, metofluthrin, cinerin II, transfluthrin, jasmolin II, cyphenothrin, peratrin, etofenprox, momfluorothrin, permethrin, silafluofen, tefluthrin, bifenthrin, or cyfluthrin.

3. The insect-repellent partition sheet according to claim 1 or 2, wherein the pyrethroid compounds are used in combination, the difference in molecular weight between the two is 40 to 160, and the mass ratio of the pyrethroid compound with a smaller molecular weight to the pyrethroid compound with a larger molecular weight is 1:3 to 3:

1.

4. The insect-repellent partition sheet according to any one of claims 1 to 3, wherein the cellulose nanofibers support the pyrethroid compound.

5. The insect-repellent partition sheet according to claim 3 , wherein the cellulose nanofibers support the pyrethroid compound (a pyrethroid compound having a smaller molecular weight).

6. The insect-repellent partition sheet according to any one of claims 1 to 5, wherein the soft vinyl chloride resin coating layer contains one or more keto / enol tautomers selected from benzotriazole tautomers, triazine tautomers, and diphenyl ketone tautomers, and the content of the keto / enol tautomers is 0.2 to 2 mass% relative to the mass of the soft vinyl chloride resin coating layer.

7. 7. The insect-repellent partition sheet according to claim 1, wherein the soft polyvinyl chloride resin coating layer contains a coloring agent, is yellow to reddish brown in color, and is transparent.

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