WO2016143810A1 - Insect repellent sheet - Google Patents

Insect repellent sheet Download PDF

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Publication number
WO2016143810A1
WO2016143810A1 PCT/JP2016/057318 JP2016057318W WO2016143810A1 WO 2016143810 A1 WO2016143810 A1 WO 2016143810A1 JP 2016057318 W JP2016057318 W JP 2016057318W WO 2016143810 A1 WO2016143810 A1 WO 2016143810A1
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WO
WIPO (PCT)
Prior art keywords
insect repellent
sheet
insect
layer
thermoplastic resin
Prior art date
Application number
PCT/JP2016/057318
Other languages
French (fr)
Japanese (ja)
Inventor
陽介 雨宮
信一 本島
中山　鶴雄
Original Assignee
株式会社Ｎｂｃメッシュテック
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Publication date
Application filed by 株式会社Ｎｂｃメッシュテック filed Critical 株式会社Ｎｂｃメッシュテック
Priority to JP2017505369A priority Critical patent/JP6705805B2/en
Publication of WO2016143810A1 publication Critical patent/WO2016143810A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
    • A01M29/12—Scaring or repelling devices, e.g. bird-scaring apparatus using odoriferous substances, e.g. aromas, pheromones or chemical agents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives

Definitions

  • the present invention relates to an insect repellent sheet having a repellent effect (insect repellent effect) against pests and the like.
  • an insect repellent sheet having repellent property against insects and the like is desired.
  • Patent Document 1 a film in which an insecticidal compound is kneaded with a synthetic resin (Patent Document 1) and a laminate (Patent Document 2) in which a pest repellent layer is provided on one surface of a sheet-like base material layer have been proposed. ing.
  • Patent Document 1 a single layer film (Patent Document 1) in which an insecticidal compound (insect repellent) is just kneaded, or a laminated film (Patent Document 2) provided with a pest repellent layer (insect repellent) provided on the surface exposed to the outside air )
  • Patent Document 2 a laminated film (Patent Document 2) provided with a pest repellent layer (insect repellent) provided on the surface exposed to the outside air )
  • the volatilization amount of the insect repellent increases, the amount of the insect repellent present on the outer surface of the film increases, so that dust tends to adhere to the insect repellent and the repellent effect against insects tends to decrease.
  • the insect repellent flows out, and in this case, there is a problem that the repellent effect against insects is not sustained.
  • the present invention has been made to solve the above-described problems, and an object thereof is to provide an insect repellent sheet that is superior in practicality.
  • the gist of the present invention is as follows.
  • An insect repellent sheet capable of releasing an insect repellent An insect repellent layer containing the insect repellent and made of a thermoplastic resin;
  • Two protective layers made of a thermoplastic resin that are in contact with the outer surface of the insect repellent layer and sandwich the insect repellent layer;
  • the insect repellent sheet wherein the crystallinity of the thermoplastic resin constituting the protective layer is equal to or less than the crystallinity of the thermoplastic resin constituting the insect repellent layer.
  • a main component of the insect repellent is a pyrethroid insect repellent.
  • a content of the insect repellent with respect to the insect repellent sheet is 0.1% by mass or more and 5% by mass or less.
  • an insect repellent sheet that exhibits an insect repellent effect while suppressing the intake of an insect repellent by a person or the like and can easily maintain the insect repellent effect.
  • This embodiment relates to an insect repellent sheet 1 from which an insect repellent can be released, and the insect repellent sheet 1 has an insect repellent layer 2 and two protective layers 3 as shown in FIG.
  • the insect repellent layer 2 has a base material made of a thermoplastic resin and an insect repellent 4.
  • the insect repellent 4 is held by the base material of the insect repellent layer 2 while being dispersed inside the base material of the insect repellent layer 2.
  • the two protective layers 3 are made of a thermoplastic resin and are in contact with the outer surface of the insect repellent layer 2 to sandwich the insect repellent layer 2.
  • the insect repellent 4 moves from the insect repellent layer 2 to the protective layer 3, and is then released from the outer surface of the protective layer 3 (the outer surface of the insect repellent sheet 1) to the outside of the insect repellent sheet 1.
  • the crystallinity of the thermoplastic resin constituting the protective layer 3 of the insect-proof sheet 1 is equal to or less than the crystallinity of the thermoplastic resin constituting the base material of the insect-proof layer 2 of the
  • the base material of the insect repellent layer 2 and the thermoplastic resin constituting the protective layer 3 can maintain the shape of the insect repellent layer 2 and the protective layer 3, and the insect repellent 4 is placed outside the insect repellent sheet 1. There is no particular limitation as long as it can be released, and it can be appropriately selected. Further, the base material of the insect repellent layer 2 and the thermoplastic resin constituting the protective layer 3 may be the same or different.
  • thermoplastic resins include polyester, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, nylon, acrylic, polyvinylidene fluoride, polyethylene tetrafluoride ethylene, polytetrafluoroethylene, and polyvinyl alcohol.
  • Polycarbonate Kevlar (registered trademark), polyacrylic acid, polymethyl methacrylate, rayon, cupra, Tencel (registered trademark), polynosic, acetate, triacetate.
  • thermoplastic resins as the thermoplastic resin constituting the base material of the insect repellent layer 2 and the protective layer 3, a crystalline thermoplastic resin is used from the viewpoint of ensuring the strength of the insect repellent layer 2 and the protective layer 3. It is done. Specific examples include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, nylon, and polyvinylidene fluoride. Among these, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and the like are more preferable as the thermoplastic resin for easily forming the insect-proof sheet 1. Furthermore, when transparency is required for the insect-proof sheet 1, it is preferable to use a crystalline thermoplastic resin having excellent transparency, such as polypropylene and polyethylene terephthalate.
  • the crystallinity of the thermoplastic resin constituting the protective layer 3 is set to be equal to or lower than the crystallinity of the thermoplastic resin constituting the base material of the insect-proof layer 2.
  • the degree of crystallinity of the thermoplastic resin can be adjusted by adjusting the temperature of the material of the thermoplastic resin and the temperature of the cast roll used when the insect-proof sheet 1 is molded to a predetermined temperature. If the relationship between the crystallinity, the thermoplastic resin material and the cast roll temperature is determined in advance, the crystallinity of the thermoplastic resin constituting the protective layer 3 is determined as the thermoplastic resin constituting the base material of the insect repellent layer 2. The degree of crystallinity can be reduced to or below.
  • the insect repellent 4 When the crystallinity of the thermoplastic resin constituting the protective layer 3 is equal to or less than the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, the insect repellent 4 mainly in the amorphous part of the protective layer 3 The insect repellent 4 can be released to the outside of the insect repellent sheet 1. Thereby, the insect-proof effect can be exhibited.
  • the crystallinity of the thermoplastic resin constituting the protective layer 3 is larger than the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, the insect repellent 4 is difficult to move through the protective layer 3. Since it becomes difficult to be released to the outside of the insect repellent sheet 1, the insect repellent effect tends to be lowered.
  • the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2 is preferably 40% or more and 100% or less.
  • the degree of crystallinity of the thermoplastic resin constituting the protective layer 3 may be less than or equal to the degree of crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, specifically 40% or more and 100% or less.
  • the crystallinity (40% or more, 100% or less) of the thermoplastic resin constituting the base material of the insect repellent layer 2 is preferably set to be equal to or less.
  • the crystallinity degree of the thermoplastic resin which comprises the base material of the insect repellent layer 2 and the protective layer 3 can be measured by the powder X-ray diffraction method, for example.
  • the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2 is such that the heat constituting the base material of the single insect repellent layer 2 (sheet) formed under the same conditions as the conditions for forming the insect repellent layer 2 is used. It can be regarded as the same as the crystallinity of the plastic resin.
  • the insect repellent 4 held in the insect repellent layer 2 is not particularly limited as long as the insect repellent layer 4 remains in the insect repellent layer 2 when the insect repellent sheet 1 is melt-kneaded and molded, and can be appropriately selected by those skilled in the art.
  • the microencapsulated insect repellent 4 can be used, or the insect repellent 4 can be supported on a porous material.
  • microencapsulated insect repellent 4 is obtained by filling the microcapsule with the insect repellent 4 as a liquid compound.
  • insect repellent sheet 1 is melt-kneaded and molded using a crystalline thermoplastic resin, the insect repellent 4 moves to the amorphous part of the thermoplastic resin, and the insect repellent 4 that does not remain in the amorphous part is repelled by the insect repellent. Bleed out to the outer surface of the sheet 1 and evaporated to the outside of the insect-proof sheet 1.
  • tackiness occurs and it becomes difficult to mold, or more than the necessary amount of the insect repellent 4 is required at the time of melt kneading.
  • the insect repellent 4 as a liquid compound is retained in the microcapsule during melt kneading, and the insect repellent 4 can be prevented from migrating to the amorphous part of the thermoplastic resin. Therefore, the insect repellent 4 can hardly bleed out to the outer surface of the insect repellent sheet 1. Thereby, while being able to make it hard to generate
  • the insect repellent 4 of this embodiment is preferably contained in the insect repellent sheet 1 as a liquid compound.
  • the insecticide 4 that is a liquid compound it becomes possible to add the insecticide 4 to the insect-repellent layer 2 in a stable state, and to easily adjust the diffusion rate of the insect-repellent 4 inside the insect-repellent sheet 1.
  • the main component of the insect repellent 4 is not particularly limited, but is preferably in a liquid form at room temperature.
  • pyrethroids such as pyrethrin, cinerine, jasmolin, allethrin, resmethrin, fenvalerate and permethrin, cyclic diene insecticides such as toxaphene and benzoepin, organophosphorus insecticides such as malathion and fenitrothion, carbaryl, Carbamate insect repellents such as mesomil and promecarb can be mentioned.
  • These insect repellents can be used alone or in combination of two or more.
  • pyrethroid insect repellents that have excellent repellency and rapid action and are less likely to show acute toxicity can be suitably used.
  • permethrin and etofenprox are preferred because they tend to exhibit an insect repellent effect at a low concentration and easily secure safety for humans and animals.
  • the insect repellent 4 contained in the insect repellent layer 2 passes through the protective layer 3 and is released to the outside of the insect repellent sheet 1. 3, the release of the insect repellent 4 can be adjusted. This makes it easier to prevent the insect repellent 4 from diffusing to the outside of the insect repellent sheet 1 as compared with the configuration in which the insect repellent 4 is contained in the protective layer 3, thus ensuring safety for humans and animals. It is possible to extend the duration of the insect repellent effect.
  • the insect repellent sheet in which the insect repellent layer 2 including the insect repellent 4 is arranged on the outer surface or the single layer insect repellent sheet including the insect repellent 4 tackiness is generated on the outer surface of the insect repellent sheet, and the insect repellent sheet is welded, for example Processability at the time of processing becomes worse (hard to process).
  • the insect repellent sheet 1 according to the present embodiment since the insect repellent layer 2 contains the insect repellent 4 and the insect repellent 4 passes through the protective layer 3, the insect repellent 4 bleeds out on the outer surface of the insect repellent sheet 1. It can suppress and can make it hard to generate
  • insect repellent sheet is washed (for example, washed with water) to remove dust adhering to the insect repellent sheet, the insect repellent is removed together with the dust etc., and the release of the insect repellent from the insect repellent sheet is promoted, and the insect repellent effect Will be shortened.
  • the present embodiment since the bleed-out of the insect repellent 4 on the outer surface of the insect repellent sheet 1 can be suppressed, it is easy to suppress the adhesion of dust or the like to the outer surface of the insect repellent sheet 1, It is possible to suppress the release of the insect repellent 4 due to dust or the like. Moreover, since the frequency
  • the insect repellent sheet 1 of the present embodiment in which permethrin is used as the insect repellent 4 when the amount of the insect repellent 4 (permethrin) exposed on the outer surface of the insect repellent sheet 1 is measured using an acetone cleaning method, the insect repellent The amount of 4 (permethrin) can be 0.4 ⁇ g or more and 10 ⁇ g or less per 1 g of the insect-proof sheet.
  • the acetone cleaning method is a method of cleaning the outer surface of the insect-repellent sheet 1 with absorbent cotton moistened with an organic solvent such as acetone, extracting an organic solvent such as acetone from the cleaned absorbent cotton, and the insect repellent 4 in the organic solvent. Is to measure the amount of.
  • the amount of the insect repellent 4 described above is a value obtained by calculating the amount of the insect repellent 4 per 1 g of the insect repellent sheet from the measurement result of the acetone cleaning method.
  • the amount of the insect repellent 4 (permethrin) is less than 0.4 ⁇ g per 1 g of the insect repellent sheet, it becomes difficult to exert the insect repellent effect.
  • the amount of the insect repellent 4 (permethrin) exceeds 10 ⁇ g per 1 g of the insect repellent sheet, the amount of intake when the person or animal touches the insect repellent sheet 1 and ingests the insect repellent 4 released from the insect repellent sheet 1 May exceed health tolerance limits.
  • the WHO and FAO United Nations Food and Agriculture Organization
  • 0.05 mg / day / kg is set as an acceptable intake amount (ADI: Acceptable Daily Intake).
  • This value is, for example, 0.75 mg when converted to 15 kg (weight of about 3 years old) per day, and it is said that permethrin is not harmful to health even if this amount is continuously consumed.
  • the amount (maximum value) of the insect repellent 4 is 0.75 mg.
  • it depends on the thickness of the insect repellent sheet 1 it is rare for a person or the like to touch the area of the insect repellent sheet 1 corresponding to 75 g in one day, even if a product manufactured from the insect repellent sheet 1 is used. , Can prevent harm to human health.
  • the cross-sectional shape of the insect repellent sheet 1 is not particularly limited as long as the protective layer 3 covers the outer surface of the insect repellent layer 2.
  • the outer edge of the insect repellent layer 2 is exposed, but the outer edge of the insect repellent layer 2 can be covered with the protective layer 3.
  • the thickness of the insect repellent layer 2 is preferably uniform throughout the insect repellent layer 2.
  • the thickness of the protective layer 3 is preferably uniform throughout the protective layer 3.
  • the thickness of the protective layer 3 is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the insect repellent 4 becomes difficult to pass through the protective layer 3 compared to the case where the thickness of the protective layer 3 is 100 ⁇ m or less, and the insect repellent effect of the insect repellent sheet 1 is exhibited. It becomes difficult to let you.
  • the thickness of the protective layer 3 is less than 1 ⁇ m, compared to the case where the thickness of the protective layer 3 is 1 ⁇ m or more, the insect repellent 4 can easily pass through the protective layer 3 and the insect repellent effect is sustained. It becomes difficult.
  • seat 1, the thickness of the insect-proof layer 2, and the thickness of the protective layer 3 can be measured using micro soup (microscope), for example.
  • the method for manufacturing the insect-proof sheet 1 according to the present embodiment can be appropriately selected by those skilled in the art, and is not particularly limited.
  • an insect repellent 4 is filled in a thermoplastic resin constituting the base material of the insect repellent layer 2 of the insect repellent sheet 1, and the insect repellent layer 2 and the protective layer 3 are used.
  • thermoplastic resin pellets are melted by an extruder for the protective layer.
  • the melt melted in the insecticidal layer extruder and the melt melted in the protective layer extruder are passed through a multilayer T-die to form a film.
  • the insect-proof sheet 1 of this embodiment can be manufactured by sending out the obtained film
  • the crystallinity degree of the thermoplastic resin which comprises the protective layer 3 is adjusted to the heat
  • the laminated body can be heated and stretched.
  • the insect repellent layer 4 is formed by filling the thermoplastic resin with the liquid insect repellent 4, the insect repellent 4 can be dispersed in the insect repellent layer 2 without variation.
  • the insect repellent 4 may be unevenly distributed in the inside.
  • the insect repellent 4 can be filled only in the upper half of the cross section of the insect repellent layer 2.
  • the insect repellent 4 can be unevenly distributed on one surface of the insect repellent sheet 1.
  • the outer surface of the insect repellent sheet 1 on the side where the insect repellent 4 is not unevenly distributed is arranged on the crop side, and the outside of the insect repellent sheet 1 on the side where the insect repellent 4 is unevenly distributed
  • the surface can be placed on the opposite side of the crop. Thereby, the insect repellent 4 is released to the side opposite to the crop side, and the insects can be prevented from approaching the insect repellent sheet 1. Moreover, since it becomes difficult to release the insect repellent 4 to a crop, it can suppress that the insect repellent 4 adheres to a crop.
  • the content of the insect repellent 4 in the insect repellent sheet 1 is preferably 0.1% by mass or more and 10% by mass or less with respect to the insect repellent sheet 1.
  • the content of the insect repellent 4 is lower than 0.1% by mass, the insect repellent effect is lowered and the duration of the insect repellent effect is shortened as compared with the case where the content of the insect repellent 4 is 0.1% by mass or more.
  • the content of the insect repellent 4 exceeds 10% by mass, the base material of the insect repellent layer 2 and the protective layer 3 serving as the skeleton of the insect repellent sheet 1 is compared with the case where the content of the insect repellent 4 is 10% by mass or less.
  • the mass% of the insecticidal sheet 1 decreases, and the strength of the insect-proof sheet 1 decreases. Furthermore, tackiness occurs, workability is poor, and sheet creation becomes difficult. Moreover, although it depends on the thickness of the protective layer 3, as the content of the insect repellent 4 increases, the amount of the insect repellent 4 exposed on the outer surface of the insect repellent sheet 1 increases, and the intake of the insect repellent 4 by humans and animals is increased. Will increase.
  • the content of the insect repellent 4 in the insect repellent sheet 1 is more preferably 0.1% by mass or more and 5% by mass or less. When the content of the insect repellent is 0.1% by mass or more and 5% by mass or less, tackiness is less likely to occur and processing defects of the insect repellent sheet 1 are less likely to occur.
  • the insect repellent sheet 1 of the present embodiment may include a component for imparting an arbitrary function as a functional material.
  • the functional materials include titanium dioxide as a matting agent, calcium stearate as a lubricant, fine particles such as silica and alumina, hindered phenol derivatives as antioxidants, and colorants such as pigments, stabilizers and dispersions.
  • additive materials such as agents, there are functional materials such as ultraviolet shielding agents, near infrared shielding agents, antibacterial agents, antifungal agents, antistatic agents, flame retardants, weathering agents, and various catalysts.
  • the functional material is present in the insect repellent layer 2 in a dispersed manner together with the insect repellent 4, is dispersed in the protective layer 3, or adheres to the outer surface of the insect repellent sheet 1. Just do it.
  • the insect repellent sheet 1 of the present embodiment may be composed of four or more layers by using a component for imparting an arbitrary function as a functional material, different from the insect repellent layer 2 and the protective layer 3.
  • Other layers include matting agent layer, lubricant layer, antioxidant layer, colored layer, UV shielding agent layer, near infrared shielding agent layer, antibacterial agent layer, antifungal agent layer, antistatic agent layer, flame retardant layer And a weathering agent layer, a pressure-sensitive adhesive layer for applying the insect-proof sheet 1 to an application object, and a reinforcing layer for improving the strength of the sheet.
  • fine irregularities may be formed by chemically bonding inorganic fine particles to the outer surface of the insect-proof sheet 1 according to the present embodiment.
  • fine irregularities dust and the like floating in the air are less likely to adhere to the outer surface of the insect-proof sheet 1. Even when dust or the like adheres to the outer surface of the insect-proof sheet 1, only dust can be easily removed with water or the like without removing the insect-repellent agent 4 exposed on the outer surface of the insect-proof sheet 1. For this reason, it can be set as the insect-proof sheet 1 excellent in dustproof property.
  • the insect repellent sheet 1 according to the present embodiment obtained as described above can release the minimum necessary insect repellent 4 capable of exhibiting the insect repellent effect and easily ensure the duration of the insect repellent effect. Become.
  • the insect repellent sheet 1 of the present embodiment can be used for various applications such as shutter sheets for food factories, vinyl houses, clean rooms, walls of existing buildings, and window glass.
  • Example 1 Master batch pellets made of permethrin (insect repellent) and highly crystalline homopolypropylene resin were prepared. Pellets made of highly crystalline homopolypropylene resin were prepared. The melted master patch pellets and highly crystalline homopolypropylene resin were mixed to obtain a mixture containing permethrin at a predetermined content. The pellet was melted to obtain a melt. By extruding these melts and mixtures from a coextrusion T-die molding apparatus, an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin. A layered insect repellent sheet was obtained.
  • the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 2 Instead of the master batch pellet used in Example 1, a master batch pellet made of etofenprox (insect repellent) and a highly crystalline homopolypropylene resin was used. The other conditions were the same as in Example 1.
  • the insect-repellent layer made of a highly crystalline homopolypropylene resin containing etofenprox was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin.
  • a layered insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of etofenprox with respect to the obtained insect-proof sheet
  • This insect repellent sheet was used as the insect repellent sheet of Example 2.
  • Example 3 Instead of the pellet made of the high crystalline homopolypropylene resin used in Example 1, pellets made of the low crystalline random polypropylene resin were used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a low crystalline random polypropylene resin An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 ⁇ m, and the thickness of the two protective layers was 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 4 A mixture having a different permethrin content from the mixture used in Example 1 was used.
  • the thickness of the insect-proof layer in Example 1 was 190 ⁇ m, and the thicknesses of the two protective layers were both 5 ⁇ m.
  • a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1.
  • An insect repellent sheet was obtained.
  • the content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 4.
  • Example 5 A mixture having a different permethrin content from the mixture used in Example 1 was used.
  • the thickness of the insect-proof layer in Example 1 was 60 ⁇ m, and the thicknesses of the two protective layers were both 70 ⁇ m.
  • a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1.
  • An insect repellent sheet was obtained.
  • the content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 5.
  • Example 6 A mixture having a different permethrin content from the mixture used in Example 1 was used.
  • the thickness of the insect-proof layer in Example 1 was 40 ⁇ m, and the thickness of the two protective layers was 80 ⁇ m.
  • a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1.
  • An insect repellent sheet was obtained.
  • the content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 6.
  • Example 7 A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 8 A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1.
  • the insect-proof layer made of a highly crystalline homopolypropylene resin containing 0.1% permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin.
  • a three-layer insect-proof sheet was obtained.
  • the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m.
  • seat was 0.1 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 8.
  • Example 9 A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 10 A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 1 The master batch pellet used in Example 1 and the pellet made of the highly crystalline homopolypropylene resin were melted and mixed to obtain a mixture containing permethrin at a predetermined content. This mixture was extruded from a co-extrusion T-die molding apparatus to obtain an insecticidal sheet having a single layer structure made of a highly crystalline homopolypropylene resin containing permethrin. The obtained insect-proof sheet had a thickness of 200 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 2 The master batch pellets used in Example 2 and the pellets made of highly crystalline homopolypropylene resin were melted and mixed to obtain a mixture containing etofenprox at a predetermined content. This mixture was extruded from a coextrusion T-die molding apparatus to obtain an insecticidal sheet having a single layer structure made of a highly crystalline homopolypropylene resin containing etofenprox. The obtained insect-proof sheet had a thickness of 200 ⁇ m. Moreover, content of etofenprox with respect to the obtained insect-proof sheet
  • Comparative Example 3 A highly crystalline homopolypropylene resin was melted to obtain a melt. The melt was extruded from a coextrusion T-die molding apparatus to obtain a film having a single layer structure made of a highly crystalline homopolypropylene resin. The thickness of the obtained film was 200 ⁇ m. This film was used as the insect repellent sheet of Comparative Example 3.
  • the thickness of the insect repellent layer was 144 ⁇ m, and the thicknesses of the two protective layers were both 28 ⁇ m. Moreover, content of permethrin with respect to the obtained insect-proof sheet
  • Example 5 A mixture having a different permethrin content from the mixture used in Example 1 was used.
  • the material used for the insect repellent layer and the material used for the protective layer were interchanged. The conditions other than these are the same as those in Example 1, and a three-layer insect repellent in which a central layer made of a highly crystalline homopolypropylene resin is sandwiched between two outer layers made of a highly crystalline homopolypropylene resin containing permethrin.
  • a sheet was obtained.
  • the thickness of the central layer was 144 ⁇ m, and the thicknesses of the two outer layers were both 28 ⁇ m.
  • seat was 1 mass%.
  • This insect repellent sheet was used as the insect repellent sheet of Comparative Example 5.
  • the degree of crystallinity of the polypropylene resin constituting the base material of the protective layer (outer layer) for Comparative Examples 1 to 3, the base material of the insect repellent sheet is constituted.
  • the crystallinity of the polypropylene resin) was measured by a powder X-ray diffraction method.
  • the crystallinity of the polypropylene resin constituting the base material of the insect repellent layer (center layer) is such that a single insect repellent layer (sheet) is formed under the same conditions as those for forming the insect repellent layer.
  • the crystallinity of the polypropylene resin constituting the base material was determined by measuring by a powder X-ray diffraction method. The results are shown in Table 1.
  • One side surface (the surface of the protective layer on one side) of the insect repellent sheets of Examples 1 to 10 and Comparative Examples 1 to 5 was respectively wiped with absorbent cotton moistened with acetone, and acetone was extracted from the absorbent cotton.
  • the amount of the insect repellent contained in the extracted acetone was measured using a gas chromatograph mass spectrometer (GC-MS). From the measured amount of insect repellent, the amount of insect repellent (ng / cm 2 ) exposed on the surface per 1 cm 2 of insect repellent sheet was calculated.
  • the permissible daily intake for an infant weighing 15 kg calculated based on ADI is 0.75 mg when the insect repellent is permethrin, and 0.45 mg when the insect repellent is etofenprox. .
  • Safety was evaluated according to the following evaluation criteria. If the evaluation is “A”, it is judged to have excellent safety. If the evaluation is “B”, it is judged to have safety. If the evaluation is “C”, safety is given. I decided not to. The results are shown in Table 2 described later. [Evaluation criteria] A: The area when the intake allowance is more than 0.5 m 2 . B: The area when it becomes the intake allowance is 0.1 m 2 or more and 0.5 m 2 or less. C: The area when the intake allowance is less than 0.1 m 2 .
  • the surface of a fluorescent light downlight cover (round shape, diameter 17 cm) installed outdoors was covered with the insect-proof sheets of Examples 1 to 10 and Comparative Examples 1 to 5, respectively.
  • the light was turned on for 10 minutes, and after 10 minutes, the number of flying insects that had stopped on the cover covered with each insect repellent sheet was measured. All the flying insects that remained on the cover were chironomids.
  • the insect repellent sheets of Examples 1 to 10 and Comparative Examples 1 to 5 were cut into 10 cm ⁇ 10 cm, and the mixed dust was evenly placed on the upper surface (protective layer) of each cut insect repellent sheet.
  • Each insect repellent sheet carrying the mixed dust was lifted and turned over, and a predetermined number of vibrations were applied to drop unadhered mixed dust not adhering to the insect repellent sheet.
  • the weight of each insect repellent sheet before putting mixed dust and the weight of each insect repellent sheet after dropping unadhered mixed dust were measured, and the weight of the mixed dust adhering to each insect repellent sheet was calculated.
  • As the mixed dust 15 kinds of test powder 1 defined in JIS Z 8901 were used.
  • the dust adhesion suppression effect was evaluated according to the following evaluation criteria. In addition, when evaluation was "Good", it judged that it had a dust adhesion inhibitory effect. The results are shown in Table 2 described later. [Evaluation criteria] Good: The average weight of the mixed dust adhered to the insect-proof sheet is 60 mg or less. Poor: The average weight of the mixed dust adhering to the insect-proof sheet exceeds 60 mg.
  • the insect repellent sheets of Examples 1 to 10 have an evaluation result of “A” or “B” in evaluation 1 (safety evaluation) and evaluation 2 (repellency evaluation), and evaluation 3 (dust dust)
  • evaluation 1 safety evaluation
  • evaluation 2 repellent evaluation
  • evaluation 3 dust dust
  • the evaluation result of the “adhesion suppression effect” was “Good”. From this result, it can be understood that the insect-proof sheet of the present embodiment has safety, repellency, and dust adhesion suppression effects. More specifically, by controlling the insect repellent sheet of this embodiment to the above-described configuration, the amount of the insect repellent exposed on the surface of the insect repellent sheet is controlled to the minimum necessary amount that can exert the insect repellent effect. It is understood that safety can be ensured and adhesion of dust can be suppressed.
  • the insect repellent sheet of this embodiment can maintain the insect repellent effect and is difficult to produce tackiness (adhesiveness). I understand that it is easy.
  • the insect-proof sheets of Comparative Examples 1 to 5 were evaluated as “Poor” or “C” in at least one of the evaluations 1 to 3. From this result, it can be understood that the insect repellent sheets of Comparative Examples 1 to 5 do not have at least one of safety, repellency, and dust adhesion suppressing effect.
  • the insect-proof sheets of Comparative Examples 1 to 2 and 5 have an evaluation result of Evaluation 1 of “C”. From this result, it can be understood that the insect repellent is easily exposed on the surface of the insect repellent sheet in the case of the insect repellent sheet having a single layer structure or the insect repellent sheet having a three layer structure containing the insect repellent in the outer layer.
  • the insect-proof sheets of Comparative Examples 1-2 and 5 had an evaluation result of Evaluation 3 of “Poor”. As one of the causes that resulted in this, the insect repellent sheet with a single layer structure or the insect repellent sheet with a three layer structure containing an insect repellent in the outer layer, the repellent is easily exposed on the surface of the insect repellent sheet, It is thought that dust is likely to adhere.
  • the insect repellent sheet of Comparative Example 4 has an evaluation result of “C” in evaluation 2, and as shown in the result of evaluation 1, the area when the allowable intake is reached is greater than that of the insect repellent sheets of Examples 1 to 10. It was also wide. From this result, in the insect repellent sheet, the crystallization degree of the thermoplastic resin constituting the protective layer is larger than the crystallization degree of the thermoplastic resin constituting the insect repellent layer, it is difficult for the insect repellent to move through the protective layer. It can be understood that it is difficult to release the insect repellent.
  • the insect repellent sheet of Comparative Example 3 has the smallest amount of adhering mixed dust in Evaluation 3, which is considered to be caused by the fact that the insect repellent sheet does not contain an insect repellent.
  • insect repellent sheets of Examples 1 to 9 having an insect repellent content of 0.1% by mass or more with respect to the insect repellent sheet have an insect repellent content of less than 0.1% by mass (0.01% by mass).
  • insect repellent sheet of Example 10 the repelling rate was improved by 11% or more. From this result, the insect repellent sheet having an insect repellent content of 0.1% by mass or more is more likely to exert the insect repellent effect as compared with the insect repellent sheet having an insect repellent content of less than 0.1% by mass. Can understand.
  • insect repellent sheet 2 insect repellent layer 3: protective layer 4: insect repellent

Abstract

[Problem] To exhibit an insect-repelling effect while minimizing insect repellent intake by people, etc., and to prolong said insect-repelling effect. [Solution] This insect repellent sheet (1), which can emit an insect repellent, comprises an insect-repelling layer (2) which contains an insect repellent and which is formed from a thermoplastic resin, and two protective layers (3) which contact the outer surfaces of and cover the insect-repelling layer and which are formed from a thermoplastic resin. The crystallinity of the thermoplastic resin configuring the protective layers is less than or equal to the crystallinity of the thermoplastic resin configuring the insect-repelling layer.

Description

防虫シートInsect repellent sheet
　本発明は、害虫等に対する忌避効果（防虫効果）を有する防虫シートに関する。 The present invention relates to an insect repellent sheet having a repellent effect (insect repellent effect) against pests and the like.
　従来、工場等の照明として蛍光灯が普及したため、虫類の建物内への侵入による品質トラブルの発生や作業への支障が無視できない問題となってきた。 Conventionally, since fluorescent lamps have been widely used as lighting in factories and the like, it has become a problem that quality troubles and troubles caused by invading insects into buildings cannot be ignored.
　そこで、虫の侵入を抑制するため、虫等に対する忌避性を有する防虫シートが望まれている。 Therefore, in order to suppress the invasion of insects, an insect repellent sheet having repellent property against insects and the like is desired.
　これらを解決する方法として、合成樹脂に殺虫性化合物を混練したフィルム（特許文献１）や、シート状基材層の一方の面に害虫忌避層を設けた積層体（特許文献２）が提案されている。 As a method for solving these problems, a film in which an insecticidal compound is kneaded with a synthetic resin (Patent Document 1) and a laminate (Patent Document 2) in which a pest repellent layer is provided on one surface of a sheet-like base material layer have been proposed. ing.
実開昭５９－１９３２８３号公報Japanese Utility Model Publication No.59-193283 特開２００５－００２００２号公報Japanese Patent Laid-Open No. 2005-002002
　しかしながら、殺虫性化合物（防虫剤）が練りこまれただけの単層フィルム（特許文献１）や、害虫忌避層（防虫剤）が外気に曝される面に設けられた積層フィルム（特許文献２）では、単位時間あたりの防虫剤の揮発量が多くなるため、防虫効果は高くなるが、人等に対する安全性は低く、また虫に対する忌避効果が長期間持続しない。 However, a single layer film (Patent Document 1) in which an insecticidal compound (insect repellent) is just kneaded, or a laminated film (Patent Document 2) provided with a pest repellent layer (insect repellent) provided on the surface exposed to the outside air ) Increases the volatilization amount of the insect repellent per unit time, so that the insect repellent effect is high, but the safety to humans is low, and the repellent effect against insects does not last for a long time.
　また、防虫剤の揮発量が多くなると、フィルムの外表面に存在する防虫剤の量が多くなるため、塵埃が防虫剤に付着し易くなり、虫に対する忌避効果が低下しやすい。一方で、塵埃を除去するために水洗いすると防虫剤が流出し、この場合も虫に対する忌避効果が持続しないという問題がある。 Also, when the volatilization amount of the insect repellent increases, the amount of the insect repellent present on the outer surface of the film increases, so that dust tends to adhere to the insect repellent and the repellent effect against insects tends to decrease. On the other hand, when washing with water to remove dust, the insect repellent flows out, and in this case, there is a problem that the repellent effect against insects is not sustained.
　さらに、防虫剤がフィルムの外表面に存在するとタック性が出て、当該フィルムを加工すると加工性に劣るという問題がある。そのため、これらの点を考慮すると、従来提案されているフィルムは実用性が十分であるものではなかった。 Furthermore, when the insect repellent is present on the outer surface of the film, tackiness appears, and when the film is processed, the processability is inferior. Therefore, considering these points, the conventionally proposed film has not been sufficiently practical.
　本発明は、上記の課題を解決するためになされたものであって、実用性により優れた防虫シートを提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object thereof is to provide an insect repellent sheet that is superior in practicality.
　本発明の要旨は以下のとおりである。
[１]　防虫剤を放出可能である防虫シートであって、
　前記防虫剤を含有し、熱可塑性樹脂からなる防虫層と、
　前記防虫層の外面と接触して前記防虫層を挟む、熱可塑性樹脂からなる２つの保護層と、を有し、
　前記保護層を構成する熱可塑性樹脂の結晶化度が、前記防虫層を構成する熱可塑性樹脂の結晶化度以下であることを特徴とする防虫シート。
[２]　前記防虫剤の主成分がピレスロイド系防虫剤であることを特徴とする[１]に記載の防虫シート。
[３]　前記ピレスロイド系防虫剤がペルメトリンまたはエトフェンプロックスの少なくとも１種類以上であることを特徴とする[２]に記載の防虫シート。
[４]　前記各保護層の厚さが１μｍ以上、１００μｍ以下であることを特徴とする[１]から[３]のいずれか一つに記載の防虫シート。
[５]　前記防虫シートに対する前記防虫剤の含有量が０．１質量％以上、５質量％以下であることを特徴とする[１]から[４]のいずれか一つに記載の防虫シート。 The gist of the present invention is as follows.
[1] An insect repellent sheet capable of releasing an insect repellent,
An insect repellent layer containing the insect repellent and made of a thermoplastic resin;
Two protective layers made of a thermoplastic resin that are in contact with the outer surface of the insect repellent layer and sandwich the insect repellent layer;
The insect repellent sheet, wherein the crystallinity of the thermoplastic resin constituting the protective layer is equal to or less than the crystallinity of the thermoplastic resin constituting the insect repellent layer.
[2] The insect repellent sheet according to [1], wherein a main component of the insect repellent is a pyrethroid insect repellent.
[3] The insect repellent sheet according to [2], wherein the pyrethroid insecticide is at least one of permethrin or etofenprox.
[4] The insect repellent sheet according to any one of [1] to [3], wherein the thickness of each protective layer is 1 μm or more and 100 μm or less.
[5] The insect repellent sheet according to any one of [1] to [4], wherein a content of the insect repellent with respect to the insect repellent sheet is 0.1% by mass or more and 5% by mass or less.
　本発明によれば、人などによる防虫剤の摂取量を抑制しながら防虫効果を発揮させるとともに、防虫効果を持続させやすい防虫シートを提供することが可能となる。 According to the present invention, it is possible to provide an insect repellent sheet that exhibits an insect repellent effect while suppressing the intake of an insect repellent by a person or the like and can easily maintain the insect repellent effect.
防虫シートの構造を示す概略図である。It is the schematic which shows the structure of an insect-proof sheet. 防虫層において、防虫剤が偏在した防虫シートの断面図である。It is sectional drawing of the insect repellent sheet in which the insect repellent was unevenly distributed in the insect repellent layer.
　以下に、本発明の実施形態の１つについて、図１を用いて詳細に説明する。 Hereinafter, one embodiment of the present invention will be described in detail with reference to FIG.
　本実施形態は、防虫剤を放出可能である防虫シート１に関し、図１に示すように、防虫シート１は、防虫層２および２つの保護層３を有する。防虫層２は、熱可塑性樹脂からなる母材と、防虫剤４とを有する。防虫剤４は、防虫層２の母材内部に分散された状態において、防虫層２の母材によって保持されている。２つの保護層３は、熱可塑性樹脂からなり、防虫層２の外面と接触して防虫層２を挟んでいる。防虫剤４は、防虫層２から保護層３に移動した後、保護層３の外面（防虫シート１の外表面）から防虫シート１の外部に放出される。ここで、防虫シート１の保護層３を構成する熱可塑性樹脂の結晶化度は、防虫シート１の防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下である。 This embodiment relates to an insect repellent sheet 1 from which an insect repellent can be released, and the insect repellent sheet 1 has an insect repellent layer 2 and two protective layers 3 as shown in FIG. The insect repellent layer 2 has a base material made of a thermoplastic resin and an insect repellent 4. The insect repellent 4 is held by the base material of the insect repellent layer 2 while being dispersed inside the base material of the insect repellent layer 2. The two protective layers 3 are made of a thermoplastic resin and are in contact with the outer surface of the insect repellent layer 2 to sandwich the insect repellent layer 2. The insect repellent 4 moves from the insect repellent layer 2 to the protective layer 3, and is then released from the outer surface of the protective layer 3 (the outer surface of the insect repellent sheet 1) to the outside of the insect repellent sheet 1. Here, the crystallinity of the thermoplastic resin constituting the protective layer 3 of the insect-proof sheet 1 is equal to or less than the crystallinity of the thermoplastic resin constituting the base material of the insect-proof layer 2 of the insect-proof sheet 1.
　本実施形態の防虫シート１において、防虫層２の母材および保護層３を構成する熱可塑性樹脂は、防虫層２および保護層３の形状を維持でき、防虫剤４を防虫シート１の外部に放出させることができればよく、特に限定されず適宜選択できる。また、防虫層２の母材と保護層３を構成する熱可塑性樹脂は、同一でも異なっていてもよい。熱可塑性樹脂として、例えば、ポリエステル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリテトラメチレンテレフタレート、ナイロン、アクリル、ポリフッ化ビニリデン、ポリエチレン四フッ化エチレン、ポリテトラフルオロエチレン、ポリビニルアルコール、ポリカーボネート、ケブラー（登録商標）、ポリアクリル酸、ポリメタクリル酸メチル、レーヨン、キュプラ、テンセル（登録商標）、ポリノジック、アセテート、トリアセテートがある。これらの熱可塑性樹脂のうち、防虫層２の母材および保護層３を構成する熱可塑性樹脂としては、防虫層２や保護層３の強度を確保する面から、結晶性の熱可塑性樹脂が用いられる。具体的には、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ナイロン、ポリフッ化ビニリデンなどが挙げられる。この中でも、防虫シート１を成形しやすい熱可塑性樹脂として、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどがより好ましい。さらに、防虫シート１に透明性が要求される場合、ポリプロピレン、ポリエチレンテレフタレートなどの透明性に優れた結晶性の熱可塑性樹脂を用いることが好ましい。 In the insect repellent sheet 1 of this embodiment, the base material of the insect repellent layer 2 and the thermoplastic resin constituting the protective layer 3 can maintain the shape of the insect repellent layer 2 and the protective layer 3, and the insect repellent 4 is placed outside the insect repellent sheet 1. There is no particular limitation as long as it can be released, and it can be appropriately selected. Further, the base material of the insect repellent layer 2 and the thermoplastic resin constituting the protective layer 3 may be the same or different. Examples of thermoplastic resins include polyester, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, nylon, acrylic, polyvinylidene fluoride, polyethylene tetrafluoride ethylene, polytetrafluoroethylene, and polyvinyl alcohol. , Polycarbonate, Kevlar (registered trademark), polyacrylic acid, polymethyl methacrylate, rayon, cupra, Tencel (registered trademark), polynosic, acetate, triacetate. Among these thermoplastic resins, as the thermoplastic resin constituting the base material of the insect repellent layer 2 and the protective layer 3, a crystalline thermoplastic resin is used from the viewpoint of ensuring the strength of the insect repellent layer 2 and the protective layer 3. It is done. Specific examples include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, nylon, and polyvinylidene fluoride. Among these, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and the like are more preferable as the thermoplastic resin for easily forming the insect-proof sheet 1. Furthermore, when transparency is required for the insect-proof sheet 1, it is preferable to use a crystalline thermoplastic resin having excellent transparency, such as polypropylene and polyethylene terephthalate.
　本実施形態では、保護層３を構成する熱可塑性樹脂の結晶化度を、防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下にしている。熱可塑性樹脂の結晶化度は、熱可塑性樹脂の材料や、防虫シート１を成形する際に用いられるキャストロールの温度を所定の温度に調整することで、調整することが可能である。結晶化度、熱可塑性樹脂の材料及びキャストロールの温度の関係を予め求めておけば、保護層３を構成する熱可塑性樹脂の結晶化度を、防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下にすることができる。 In this embodiment, the crystallinity of the thermoplastic resin constituting the protective layer 3 is set to be equal to or lower than the crystallinity of the thermoplastic resin constituting the base material of the insect-proof layer 2. The degree of crystallinity of the thermoplastic resin can be adjusted by adjusting the temperature of the material of the thermoplastic resin and the temperature of the cast roll used when the insect-proof sheet 1 is molded to a predetermined temperature. If the relationship between the crystallinity, the thermoplastic resin material and the cast roll temperature is determined in advance, the crystallinity of the thermoplastic resin constituting the protective layer 3 is determined as the thermoplastic resin constituting the base material of the insect repellent layer 2. The degree of crystallinity can be reduced to or below.
　保護層３を構成する熱可塑性樹脂の結晶化度が、防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下であると、主に保護層３の非晶部において、防虫剤４を移動させやすくし、防虫シート１の外部に防虫剤４を放出させることができる。これにより、防虫効果を発揮させることができる。ここで、保護層３を構成する熱可塑性樹脂の結晶化度が、防虫層２の母材を構成する熱可塑性樹脂の結晶化度より大きい場合、防虫剤４が、保護層３を移動しにくくなり、防虫シート１の外部に放出されにくくなるため、防虫効果が低下しやすくなる。 When the crystallinity of the thermoplastic resin constituting the protective layer 3 is equal to or less than the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, the insect repellent 4 mainly in the amorphous part of the protective layer 3 The insect repellent 4 can be released to the outside of the insect repellent sheet 1. Thereby, the insect-proof effect can be exhibited. Here, when the crystallinity of the thermoplastic resin constituting the protective layer 3 is larger than the crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, the insect repellent 4 is difficult to move through the protective layer 3. Since it becomes difficult to be released to the outside of the insect repellent sheet 1, the insect repellent effect tends to be lowered.
　防虫層２の母材を構成する熱可塑性樹脂の結晶化度は、４０％以上、１００％以下が好ましい。保護層３を構成する熱可塑性樹脂の結晶化度は、防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下にすればよく、具体的には、４０％以上、１００％以下の範囲内において、防虫層２の母材を構成する熱可塑性樹脂の結晶化度（４０％以上、１００％以下）以下とすることが好ましい。なお、防虫層２及び保護層３の母材を構成する熱可塑性樹脂の結晶化度は、例えば、粉末Ｘ線回折法により測定することができる。また、防虫層２の母材を構成する熱可塑性樹脂の結晶化度は、防虫層２を形成する条件と同様の条件で形成した単層の防虫層２（シート）の母材を構成する熱可塑性樹脂の結晶化度と同一とみなすことができる。 The crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2 is preferably 40% or more and 100% or less. The degree of crystallinity of the thermoplastic resin constituting the protective layer 3 may be less than or equal to the degree of crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2, specifically 40% or more and 100% or less. Within the range, the crystallinity (40% or more, 100% or less) of the thermoplastic resin constituting the base material of the insect repellent layer 2 is preferably set to be equal to or less. In addition, the crystallinity degree of the thermoplastic resin which comprises the base material of the insect repellent layer 2 and the protective layer 3 can be measured by the powder X-ray diffraction method, for example. The crystallinity of the thermoplastic resin constituting the base material of the insect repellent layer 2 is such that the heat constituting the base material of the single insect repellent layer 2 (sheet) formed under the same conditions as the conditions for forming the insect repellent layer 2 is used. It can be regarded as the same as the crystallinity of the plastic resin.
　防虫層２に保持される防虫剤４は、防虫シート１を溶融混練して成形する際に防虫層２に防虫剤４が残ればよく、特に限定されず、当業者が適宜選択できる。例えば、マイクロカプセル化した防虫剤４を用いたり、多孔質物質に防虫剤４を担持したりすることができる。 The insect repellent 4 held in the insect repellent layer 2 is not particularly limited as long as the insect repellent layer 4 remains in the insect repellent layer 2 when the insect repellent sheet 1 is melt-kneaded and molded, and can be appropriately selected by those skilled in the art. For example, the microencapsulated insect repellent 4 can be used, or the insect repellent 4 can be supported on a porous material.
　本実施形態においては、マイクロカプセル化した防虫剤４を用いることが好ましい。マイクロカプセル化した防虫剤４とは、防虫剤４が液状化合物としてマイクロカプセル内に充填されたものである。結晶性の熱可塑性樹脂を用いて、防虫シート１を溶融混練して成形する場合には、防虫剤４が熱可塑性樹脂の非晶部に移行し、非晶部に留まれない防虫剤４が防虫シート１の外表面にブリードアウトして、防虫シート１の外部に蒸発してしまう。このため、タック性（粘着性）が発生して成形し難くなったり、溶融混練のときに必要量以上の防虫剤４が必要となったりする。マイクロカプセル化した防虫剤４を用いれば、溶融混練のときに、液状化合物としての防虫剤４をマイクロカプセル内に留めて、防虫剤４が熱可塑性樹脂の非晶部に移行することを抑制できるため、防虫剤４が防虫シート１の外表面にブリードアウトしにくくできる。これにより、タック性を発生し難くできるとともに、必要量以上の防虫剤４が用いられることを抑制できる。 In this embodiment, it is preferable to use the microencapsulated insect repellent 4. The microencapsulated insect repellent 4 is obtained by filling the microcapsule with the insect repellent 4 as a liquid compound. When the insect repellent sheet 1 is melt-kneaded and molded using a crystalline thermoplastic resin, the insect repellent 4 moves to the amorphous part of the thermoplastic resin, and the insect repellent 4 that does not remain in the amorphous part is repelled by the insect repellent. Bleed out to the outer surface of the sheet 1 and evaporated to the outside of the insect-proof sheet 1. For this reason, tackiness (adhesiveness) occurs and it becomes difficult to mold, or more than the necessary amount of the insect repellent 4 is required at the time of melt kneading. When the microencapsulated insect repellent 4 is used, the insect repellent 4 as a liquid compound is retained in the microcapsule during melt kneading, and the insect repellent 4 can be prevented from migrating to the amorphous part of the thermoplastic resin. Therefore, the insect repellent 4 can hardly bleed out to the outer surface of the insect repellent sheet 1. Thereby, while being able to make it hard to generate | occur | produce tackiness, it can suppress that the insect repellent 4 more than a required amount is used.
　本実施形態の防虫剤４は、液状化合物として防虫シート１に含まれることが好ましい。液状化合物の防虫剤４を用いることで、防虫剤４を安定した状態で防虫層２に高濃度添加することが可能となるとともに、防虫シート１の内部における防虫剤４の拡散速度を調整しやすくなる。また、防虫剤４の主成分としては、特に限定されないが、常温において液体の形態のものが好ましい。具体的には、ピレトリン、シネリン、ジャスモリン、アレスリン、レスメトリン、フェンバレラート、ペルメトリンなどのピレスロイド系防虫剤、トキサフェン、ベンゾエピンなどの環状ジエン系防虫剤、マラチオン、フェニトロチオンなどの有機リン系防虫剤、カルバリル、メソミル、プロメカルブなどのカルバメート系防虫剤などを挙げることができる。これらの防虫剤は、１種類、あるいは、２種類以上を組み合わせて用いることもできる。これらの防虫剤の中でも、優れた忌避性と速効性を有し、しかも急性毒性を示しにくいピレスロイド系防虫剤を好適に用いることができる。また、ピレスロイド系の中でも、低濃度で防虫効果を発揮しやすいとともに、人や動物に対する安全性を確保しやすいペルメトリンやエトフェンプロックスが好適である。 The insect repellent 4 of this embodiment is preferably contained in the insect repellent sheet 1 as a liquid compound. By using the insecticide 4 that is a liquid compound, it becomes possible to add the insecticide 4 to the insect-repellent layer 2 in a stable state, and to easily adjust the diffusion rate of the insect-repellent 4 inside the insect-repellent sheet 1. Become. Further, the main component of the insect repellent 4 is not particularly limited, but is preferably in a liquid form at room temperature. Specifically, pyrethroids such as pyrethrin, cinerine, jasmolin, allethrin, resmethrin, fenvalerate and permethrin, cyclic diene insecticides such as toxaphene and benzoepin, organophosphorus insecticides such as malathion and fenitrothion, carbaryl, Carbamate insect repellents such as mesomil and promecarb can be mentioned. These insect repellents can be used alone or in combination of two or more. Among these insect repellents, pyrethroid insect repellents that have excellent repellency and rapid action and are less likely to show acute toxicity can be suitably used. Among pyrethroids, permethrin and etofenprox are preferred because they tend to exhibit an insect repellent effect at a low concentration and easily secure safety for humans and animals.
　本実施形態では、防虫層２および保護層３を有する防虫シート１において、防虫層２に含有された防虫剤４が保護層３を通過して防虫シート１の外部に放出されるため、保護層３において、防虫剤４の放出を調整可能である。これにより、保護層３に防虫剤４を含有させた構成と比較して、防虫剤４が防虫シート１の外部に拡散することを抑制しやすくなるため、人や動物に対して安全性を確保できるとともに、防虫効果の持続時間を延ばすことが可能となる。 In this embodiment, in the insect repellent sheet 1 having the insect repellent layer 2 and the protective layer 3, the insect repellent 4 contained in the insect repellent layer 2 passes through the protective layer 3 and is released to the outside of the insect repellent sheet 1. 3, the release of the insect repellent 4 can be adjusted. This makes it easier to prevent the insect repellent 4 from diffusing to the outside of the insect repellent sheet 1 as compared with the configuration in which the insect repellent 4 is contained in the protective layer 3, thus ensuring safety for humans and animals. It is possible to extend the duration of the insect repellent effect.
　防虫剤４を含む防虫層２が外表面に配置された防虫シート、あるいは防虫剤４を含む単層の防虫シートでは、防虫シートの外表面にタック性が発生して、防虫シートを例えば、溶着加工する際などの加工性が悪く（加工し難く）なる。一方、本実施形態に係る防虫シート１では、防虫層２に防虫剤４を含有させて、防虫剤４が保護層３を通過するため、防虫シート１の外表面における防虫剤４のブリードアウトを抑制でき、タック性を発生させにくくできる。そのため、防虫シート１を加工し易い。 In the insect repellent sheet in which the insect repellent layer 2 including the insect repellent 4 is arranged on the outer surface or the single layer insect repellent sheet including the insect repellent 4, tackiness is generated on the outer surface of the insect repellent sheet, and the insect repellent sheet is welded, for example Processability at the time of processing becomes worse (hard to process). On the other hand, in the insect repellent sheet 1 according to the present embodiment, since the insect repellent layer 2 contains the insect repellent 4 and the insect repellent 4 passes through the protective layer 3, the insect repellent 4 bleeds out on the outer surface of the insect repellent sheet 1. It can suppress and can make it hard to generate | occur | produce tackiness. Therefore, it is easy to process the insect-proof sheet 1.
　また、防虫シートの外表面にタック性が発生しやすいと、防虫シートの外表面に塵埃等が付着し易くなる。防虫シートの外表面に付着した塵埃等は、防虫シートからの防虫剤の放出を阻害し、防虫効果を低減させるため、好ましくない。また、防虫シートに付着した塵埃等を除去するために防虫シートを洗浄（例えば、水洗）すると、塵埃等とともに防虫剤が除去され、防虫シートからの防虫剤の放出が促進されてしまい、防虫効果の持続時間が短縮されてしまう。 Also, if tackiness is likely to occur on the outer surface of the insect-proof sheet, dust or the like is likely to adhere to the outer surface of the insect-proof sheet. Dust and the like adhering to the outer surface of the insect repellent sheet are not preferable because they inhibit the release of the insect repellent from the insect repellent sheet and reduce the insect repellent effect. In addition, if the insect repellent sheet is washed (for example, washed with water) to remove dust adhering to the insect repellent sheet, the insect repellent is removed together with the dust etc., and the release of the insect repellent from the insect repellent sheet is promoted, and the insect repellent effect Will be shortened.
　一方、本実施形態では、上述したように、防虫シート１の外表面における防虫剤４のブリードアウトを抑制できるため、防虫シート１の外表面に塵埃等が付着することを抑制しやすくなるとともに、塵埃等によって防虫剤４の放出が阻害されることを抑制できる。また、防虫シート１を洗浄する回数も抑えられるため、洗浄と共に防虫剤４が除去されることを抑制でき、防虫効果の持続時間を延ばすことができる。 On the other hand, in the present embodiment, as described above, since the bleed-out of the insect repellent 4 on the outer surface of the insect repellent sheet 1 can be suppressed, it is easy to suppress the adhesion of dust or the like to the outer surface of the insect repellent sheet 1, It is possible to suppress the release of the insect repellent 4 due to dust or the like. Moreover, since the frequency | count which wash | cleans the insect repellent sheet | seat 1 is also suppressed, it can suppress that the insect repellent 4 is removed with washing | cleaning, and can extend the duration of an insect repellent effect.
　防虫剤４としてペルメトリンが用いられる本実施形態の防虫シート１によれば、アセトン洗浄法を用いて、防虫シート１の外表面に露出する防虫剤４（ペルメトリン）の量を測定したとき、防虫剤４（ペルメトリン）の量を防虫シート１ｇ当たり０．４μｇ以上、１０μｇ以下とすることができる。アセトン洗浄法とは、アセトン等の有機溶媒で湿らせた脱脂綿で防虫シート１の外表面を洗浄処理し、洗浄処理した脱脂綿からアセトン等の有機溶媒を抽出して、有機溶媒中の防虫剤４の量を測定するものである。上述した防虫剤４の量は、アセトン洗浄法の測定結果から、防虫シート１ｇ当たりの防虫剤４の量を算出した値である。 According to the insect repellent sheet 1 of the present embodiment in which permethrin is used as the insect repellent 4, when the amount of the insect repellent 4 (permethrin) exposed on the outer surface of the insect repellent sheet 1 is measured using an acetone cleaning method, the insect repellent The amount of 4 (permethrin) can be 0.4 μg or more and 10 μg or less per 1 g of the insect-proof sheet. The acetone cleaning method is a method of cleaning the outer surface of the insect-repellent sheet 1 with absorbent cotton moistened with an organic solvent such as acetone, extracting an organic solvent such as acetone from the cleaned absorbent cotton, and the insect repellent 4 in the organic solvent. Is to measure the amount of. The amount of the insect repellent 4 described above is a value obtained by calculating the amount of the insect repellent 4 per 1 g of the insect repellent sheet from the measurement result of the acetone cleaning method.
　防虫剤４（ペルメトリン）の量が防虫シート１ｇ当たり０．４μｇ未満の場合は、防虫効果を発揮させにくくなる。一方、防虫剤４（ペルメトリン）の量が防虫シート１ｇ当たり１０μｇを超えると、人や動物が防虫シート１に触れて、防虫シート１から放出された防虫剤４を摂取したときの摂取量が、健康に害を与えない許容量を超えてしまうことがある。ＷＨＯとＦＡＯ（国連食糧農業機関）では、多くの動物実験などのデータをもとに、ペルメトリンが人体に与える悪影響を調査しており、この調査結果によると、人間が一生摂取し続けても影響のない量、すなわち、許容摂取量（ＡＤＩ：Acceptable Daily Intake）として、「０．０５ｍｇ／ｄａｙ／ｋｇ」を設定している。この値は、例えば１５ｋｇ（３歳児くらいの体重）の１日当たりに換算すると０．７５ｍｇとなり、ペルメトリンに関しては、これだけの量を摂取し続けても、健康に害はないとされている。本実施形態によれば、７５ｇの防虫シート１を使用したときに、防虫剤４の量（最大値）が０．７５ｍｇとなる。防虫シート１の厚さにもよるが、人等が、１日のうちで７５ｇに相当する防虫シート１の面積に触れることは稀であり、防虫シート１から製造された製品を使用しても、人などの健康に害を与えることを防止できる。 When the amount of the insect repellent 4 (permethrin) is less than 0.4 μg per 1 g of the insect repellent sheet, it becomes difficult to exert the insect repellent effect. On the other hand, when the amount of the insect repellent 4 (permethrin) exceeds 10 μg per 1 g of the insect repellent sheet, the amount of intake when the person or animal touches the insect repellent sheet 1 and ingests the insect repellent 4 released from the insect repellent sheet 1 May exceed health tolerance limits. The WHO and FAO (United Nations Food and Agriculture Organization) are investigating the negative effects of permethrin on the human body based on data from many animal experiments. “0.05 mg / day / kg” is set as an acceptable intake amount (ADI: Acceptable Daily Intake). This value is, for example, 0.75 mg when converted to 15 kg (weight of about 3 years old) per day, and it is said that permethrin is not harmful to health even if this amount is continuously consumed. According to this embodiment, when 75 g of the insect repellent sheet 1 is used, the amount (maximum value) of the insect repellent 4 is 0.75 mg. Although it depends on the thickness of the insect repellent sheet 1, it is rare for a person or the like to touch the area of the insect repellent sheet 1 corresponding to 75 g in one day, even if a product manufactured from the insect repellent sheet 1 is used. , Can prevent harm to human health.
　また、防虫剤４の量が増えると、防虫シート１の外表面にタック性が発生することにより、加工性に劣ったり、塵埃が防虫シート１に付着しやすくなって防虫効果が低下したりする。 Further, when the amount of the insect repellent 4 is increased, tackiness is generated on the outer surface of the insect repellent sheet 1, so that the processability is inferior or dust easily adheres to the insect repellent sheet 1 and the insect repellent effect is reduced. .
　本実施形態では、防虫シート１の断面形状は、防虫層２の外面を保護層３が覆う形状であれば特に限定されるものではない。本実施形態の防虫シート１では、図１に示すように、防虫層２の外縁が露出しているが、防虫層２の外縁を保護層３によって覆うこともできる。防虫層２の厚さは、防虫層２の全体において、均一であることが好ましい。また、保護層３の厚さは、保護層３の全体において、均一であることが好ましい。保護層３の厚さは１μｍ以上、１００μｍ以下であることが好ましい。保護層３の厚さが１００μｍを超えると、保護層３の厚さが１００μｍ以下である場合と比較して、防虫剤４が保護層３を通過し難くなり、防虫シート１の防虫効果を発揮させにくくなる。一方、保護層３の厚さが１μｍ未満である場合、保護層３の厚さが１μｍ以上である場合と比較して、防虫剤４が保護層３を通過しやすくなり、防虫効果が持続しにくくなる。なお、防虫シート１の厚さ、防虫層２の厚さ及び保護層３の厚さは、例えば、マイクロスープ（顕微鏡）を用いて測定することができる。 In this embodiment, the cross-sectional shape of the insect repellent sheet 1 is not particularly limited as long as the protective layer 3 covers the outer surface of the insect repellent layer 2. In the insect repellent sheet 1 of the present embodiment, as shown in FIG. 1, the outer edge of the insect repellent layer 2 is exposed, but the outer edge of the insect repellent layer 2 can be covered with the protective layer 3. The thickness of the insect repellent layer 2 is preferably uniform throughout the insect repellent layer 2. The thickness of the protective layer 3 is preferably uniform throughout the protective layer 3. The thickness of the protective layer 3 is preferably 1 μm or more and 100 μm or less. When the thickness of the protective layer 3 exceeds 100 μm, the insect repellent 4 becomes difficult to pass through the protective layer 3 compared to the case where the thickness of the protective layer 3 is 100 μm or less, and the insect repellent effect of the insect repellent sheet 1 is exhibited. It becomes difficult to let you. On the other hand, when the thickness of the protective layer 3 is less than 1 μm, compared to the case where the thickness of the protective layer 3 is 1 μm or more, the insect repellent 4 can easily pass through the protective layer 3 and the insect repellent effect is sustained. It becomes difficult. In addition, the thickness of the insect-proof sheet | seat 1, the thickness of the insect-proof layer 2, and the thickness of the protective layer 3 can be measured using micro soup (microscope), for example.
　本実施形態に係る防虫シート１の製造方法は、当業者が適宜選択することができ、特に限定されない。例えば、防虫シート１の合理的かつ安価な製造方法として、防虫シート１の防虫層２の母材を構成する熱可塑性樹脂中に防虫剤４を充填しておき、防虫層２および保護層３をそれぞれ溶融押出機を用いて混練して、多層ダイを用いて成形する方法がある。具体的には、液状の防虫剤４を含有した熱可塑性樹脂などのペレットでマスターバッチペレットを予め製造し、マスターバッチペレットと同じ熱可塑性樹脂のペレットをマスターバッチペレットと共に一定の割合で混合して防虫層用の押出機にて溶融する。同時に熱可塑性樹脂のペレットを保護層用の押出機にて溶融する。防虫層用の押出機にて溶融された溶融物と保護層用の押出機にて溶融された溶融物を多層のＴダイに通して製膜する。そして、得られた膜をキャストロールで送り出すことで、本実施形態の防虫シート１を製造することができる。なお、防虫シート１成形の際に用いられるキャストロールの温度を所定の温度に調整することで、保護層３を構成する熱可塑性樹脂の結晶化度を、防虫層２の母材を構成する熱可塑性樹脂の結晶化度以下にすることができる。 The method for manufacturing the insect-proof sheet 1 according to the present embodiment can be appropriately selected by those skilled in the art, and is not particularly limited. For example, as a rational and inexpensive method for manufacturing the insect repellent sheet 1, an insect repellent 4 is filled in a thermoplastic resin constituting the base material of the insect repellent layer 2 of the insect repellent sheet 1, and the insect repellent layer 2 and the protective layer 3 are used. There is a method of kneading each using a melt extruder and molding using a multilayer die. Specifically, master batch pellets are manufactured in advance using pellets of thermoplastic resin or the like containing the liquid insect repellent 4, and the same thermoplastic resin pellets as the master batch pellets are mixed together with the master batch pellets at a certain ratio. Melt in an insect repellent extruder. At the same time, the thermoplastic resin pellets are melted by an extruder for the protective layer. The melt melted in the insecticidal layer extruder and the melt melted in the protective layer extruder are passed through a multilayer T-die to form a film. And the insect-proof sheet 1 of this embodiment can be manufactured by sending out the obtained film | membrane with a cast roll. In addition, the crystallinity degree of the thermoplastic resin which comprises the protective layer 3 is adjusted to the heat | fever which comprises the base material of the insect-proof layer 2 by adjusting the temperature of the cast roll used at the time of shaping | molding the insect-proof sheet 1 to predetermined | prescribed temperature. It can be made below the crystallinity degree of a plastic resin.
　ここで、防虫層２に保護層３を積層して積層体を製造した後、この積層体を加熱延伸することができる。 Here, after the protective layer 3 is laminated on the insect repellent layer 2 to produce a laminated body, the laminated body can be heated and stretched.
　熱可塑性樹脂に液状の防虫剤４を充填して防虫層２を形成する場合、防虫剤４を防虫層２にバラつきなく分散させることができるが、他の防虫層２の形態として、防虫層２の内部に防虫剤４が偏在するようにしてもよい。例えば、図２に示すように、防虫層２の断面の上半分においてのみ防虫剤４を充填させることができる。例えば、この防虫層２を備えた防虫シート１を農業用として使用する際、防虫シート１の片側の面に防虫剤４を偏在させることができる。防虫シート１を用いて作物を覆うとき、防虫剤４が偏在していない側の防虫シート１の外表面を作物の側に配置し、防虫剤４が偏在している側の防虫シート１の外表面を作物の側とは反対側に配置することができる。これにより、作物の側とは反対側に防虫剤４を放出させて、防虫シート１に虫が近づくことを抑制できる。また、作物には防虫剤４が放出されにくくなるため、作物に防虫剤４が付着することを抑制できる。 In the case where the insect repellent layer 4 is formed by filling the thermoplastic resin with the liquid insect repellent 4, the insect repellent 4 can be dispersed in the insect repellent layer 2 without variation. The insect repellent 4 may be unevenly distributed in the inside. For example, as shown in FIG. 2, the insect repellent 4 can be filled only in the upper half of the cross section of the insect repellent layer 2. For example, when the insect repellent sheet 1 having the insect repellent layer 2 is used for agriculture, the insect repellent 4 can be unevenly distributed on one surface of the insect repellent sheet 1. When covering the crop with the insect repellent sheet 1, the outer surface of the insect repellent sheet 1 on the side where the insect repellent 4 is not unevenly distributed is arranged on the crop side, and the outside of the insect repellent sheet 1 on the side where the insect repellent 4 is unevenly distributed The surface can be placed on the opposite side of the crop. Thereby, the insect repellent 4 is released to the side opposite to the crop side, and the insects can be prevented from approaching the insect repellent sheet 1. Moreover, since it becomes difficult to release the insect repellent 4 to a crop, it can suppress that the insect repellent 4 adheres to a crop.
　本実施形態において、防虫シート１における防虫剤４の含有量は、防虫シート１に対し０．１質量％以上、１０質量％以下であることが好ましい。防虫剤４の含有量が０．１質量％より低いと、防虫剤４の含有量が０．１質量％以上である場合と比較して、防虫効果が低くなり、防虫効果の持続時間も短縮する。防虫剤４の含有量が１０質量％を超えると、防虫剤４の含有量が１０質量％以下である場合と比較して、防虫シート１の骨格となる防虫層２および保護層３の母材の質量％が低下し、防虫シート１の強度が低下する。さらに、タック性が生じ加工性が悪く、シート作成が困難になる。また、保護層３の厚さにもよるが、防虫剤４の含有量が多くなるほど、防虫シート１の外表面における防虫剤４の露出量が多くなり、人や動物による防虫剤４の摂取量が増えてしまう。防虫シート１における防虫剤４の含有量は、より好ましくは、０．１質量％以上、５質量％以下である。防虫剤の含有量が０．１質量％以上、５質量％以下である場合、タック性が生じ難くなり、防虫シート１の加工不良が生じ難くなる。 In the present embodiment, the content of the insect repellent 4 in the insect repellent sheet 1 is preferably 0.1% by mass or more and 10% by mass or less with respect to the insect repellent sheet 1. When the content of the insect repellent 4 is lower than 0.1% by mass, the insect repellent effect is lowered and the duration of the insect repellent effect is shortened as compared with the case where the content of the insect repellent 4 is 0.1% by mass or more. To do. When the content of the insect repellent 4 exceeds 10% by mass, the base material of the insect repellent layer 2 and the protective layer 3 serving as the skeleton of the insect repellent sheet 1 is compared with the case where the content of the insect repellent 4 is 10% by mass or less. The mass% of the insecticidal sheet 1 decreases, and the strength of the insect-proof sheet 1 decreases. Furthermore, tackiness occurs, workability is poor, and sheet creation becomes difficult. Moreover, although it depends on the thickness of the protective layer 3, as the content of the insect repellent 4 increases, the amount of the insect repellent 4 exposed on the outer surface of the insect repellent sheet 1 increases, and the intake of the insect repellent 4 by humans and animals is increased. Will increase. The content of the insect repellent 4 in the insect repellent sheet 1 is more preferably 0.1% by mass or more and 5% by mass or less. When the content of the insect repellent is 0.1% by mass or more and 5% by mass or less, tackiness is less likely to occur and processing defects of the insect repellent sheet 1 are less likely to occur.
　また、本実施形態の防虫シート１は、任意の機能を付与するための成分を機能性材料として含んでもよい。当該機能性材料としては、艶消剤としての二酸化チタン、滑剤としてのステアリン酸カルシウムや、シリカやアルミナなどの微粒子、抗酸化剤としてヒンダートフェノール誘導体、さらには顔料などの着色剤、安定剤、分散剤等の添加材料の他、紫外線遮蔽剤、近赤外線遮蔽剤、抗菌剤、防黴剤、帯電防止剤、難燃剤、耐候剤および各種触媒などの機能性材料がある。なお、この機能性材料は、防虫剤４とともに防虫層２の中に分散して存在したり、保護層３の中に分散して存在したり、防虫シート１の外表面に付着したりしていればよい。 Moreover, the insect repellent sheet 1 of the present embodiment may include a component for imparting an arbitrary function as a functional material. The functional materials include titanium dioxide as a matting agent, calcium stearate as a lubricant, fine particles such as silica and alumina, hindered phenol derivatives as antioxidants, and colorants such as pigments, stabilizers and dispersions. In addition to additive materials such as agents, there are functional materials such as ultraviolet shielding agents, near infrared shielding agents, antibacterial agents, antifungal agents, antistatic agents, flame retardants, weathering agents, and various catalysts. The functional material is present in the insect repellent layer 2 in a dispersed manner together with the insect repellent 4, is dispersed in the protective layer 3, or adheres to the outer surface of the insect repellent sheet 1. Just do it.
　また、本実施形態の防虫シート１は、任意の機能を付与するための成分を機能性材料として防虫層２や保護層３とは別の層にして４層以上にしてもよい。別の層としては、艶消剤層、滑剤層、抗酸化剤層、着色層、紫外線遮蔽剤層、近赤外線遮蔽剤層、抗菌剤層、防黴剤層、帯電防止剤層、難燃剤層、耐候剤層、防虫シート１を貼付け対象に貼付けるための粘着層、シートの強度を向上させるための補強層を挙げることができる。 Further, the insect repellent sheet 1 of the present embodiment may be composed of four or more layers by using a component for imparting an arbitrary function as a functional material, different from the insect repellent layer 2 and the protective layer 3. Other layers include matting agent layer, lubricant layer, antioxidant layer, colored layer, UV shielding agent layer, near infrared shielding agent layer, antibacterial agent layer, antifungal agent layer, antistatic agent layer, flame retardant layer And a weathering agent layer, a pressure-sensitive adhesive layer for applying the insect-proof sheet 1 to an application object, and a reinforcing layer for improving the strength of the sheet.
　また、本実施形態に係る防虫シート１の外表面に無機微粒子を化学結合させ、微細な凹凸を形成してもよい。微細な凹凸を形成することにより、空気中に浮遊している塵埃などが防虫シート１の外表面にさらに付着しにくくなる。また、塵埃などが防虫シート１の外表面に付着した場合でも、防虫シート１の外表面に露出した防虫剤４を除去することなく、水などで塵埃だけを簡単に除去できる。このため、防塵性に優れた防虫シート１とすることができる。 Further, fine irregularities may be formed by chemically bonding inorganic fine particles to the outer surface of the insect-proof sheet 1 according to the present embodiment. By forming fine irregularities, dust and the like floating in the air are less likely to adhere to the outer surface of the insect-proof sheet 1. Even when dust or the like adheres to the outer surface of the insect-proof sheet 1, only dust can be easily removed with water or the like without removing the insect-repellent agent 4 exposed on the outer surface of the insect-proof sheet 1. For this reason, it can be set as the insect-proof sheet 1 excellent in dustproof property.
　以上のようにして得られた本実施形態に係る防虫シート１は、防虫効果を発揮させることができる必要最低限の防虫剤４を放出させることができるとともに、防虫効果の持続時間を確保しやすくなる。本実施形態の防虫シート１は、食品工場向けのシャッターシート、ビニルハウス、クリーンルーム、既存の建物の壁、窓ガラスなど、様々な用途に用いることが可能である。 The insect repellent sheet 1 according to the present embodiment obtained as described above can release the minimum necessary insect repellent 4 capable of exhibiting the insect repellent effect and easily ensure the duration of the insect repellent effect. Become. The insect repellent sheet 1 of the present embodiment can be used for various applications such as shutter sheets for food factories, vinyl houses, clean rooms, walls of existing buildings, and window glass.
　次に実施例を示して、本実施形態の防虫シートについてより詳細に説明するが、本発明の技術的範囲はこれらの実施例に限定されるものではない。 Next, examples will be shown to describe the insect repellent sheet of this embodiment in more detail, but the technical scope of the present invention is not limited to these examples.
　　（実施例１）
　ペルメトリン（防虫剤）と高結晶性ホモポリプロピレン樹脂からなるマスターバッチペレットを用意した。高結晶性ホモポリプロピレン樹脂からなるペレットを用意した。溶融したマスターパッチペレットと高結晶性ホモポリプロピレン樹脂とを混合し、ペルメトリンを所定の含有量で含有する混合物を得た。ペレットを溶融し、溶融物を得た。これら溶融物及び混合物を共押出Ｔダイ成型装置から押し出すことにより、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、実施例１の防虫シートとした。 (Example 1)
Master batch pellets made of permethrin (insect repellent) and highly crystalline homopolypropylene resin were prepared. Pellets made of highly crystalline homopolypropylene resin were prepared. The melted master patch pellets and highly crystalline homopolypropylene resin were mixed to obtain a mixture containing permethrin at a predetermined content. The pellet was melted to obtain a melt. By extruding these melts and mixtures from a coextrusion T-die molding apparatus, an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin. A layered insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 1.
　　（実施例２）
　実施例１で用いたマスターバッチペレットに代えて、エトフェンプロックス（防虫剤）と高結晶性ホモポリプロピレン樹脂からなるマスターバッチペレットを用いた。これ以外の条件は、実施例１と同様の条件により、エトフェンプロックスを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するエトフェンプロックスの含有量は、１質量％であった。この防虫シートを、実施例２の防虫シートとした。 (Example 2)
Instead of the master batch pellet used in Example 1, a master batch pellet made of etofenprox (insect repellent) and a highly crystalline homopolypropylene resin was used. The other conditions were the same as in Example 1. The insect-repellent layer made of a highly crystalline homopolypropylene resin containing etofenprox was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin. A layered insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of etofenprox with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 2.
　　（実施例３）
　実施例１で用いた高結晶性ホモポリプロピレン樹脂からなるペレットに代えて、低結晶性ランダムポリプロピレン樹脂からなるペレットを用いた。これ以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、低結晶性ランダムポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、実施例３の防虫シートとした。 (Example 3)
Instead of the pellet made of the high crystalline homopolypropylene resin used in Example 1, pellets made of the low crystalline random polypropylene resin were used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a low crystalline random polypropylene resin An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thickness of the two protective layers was 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 3.
　　（実施例４）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。実施例１における防虫層の厚みを１９０μｍとし、２つの保護層の厚みを共に５μｍとした。これら以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、実施例４の防虫シートとした。 Example 4
A mixture having a different permethrin content from the mixture used in Example 1 was used. The thickness of the insect-proof layer in Example 1 was 190 μm, and the thicknesses of the two protective layers were both 5 μm. Other than these conditions, a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1. An insect repellent sheet was obtained. The content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 4.
　　（実施例５）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。実施例１における防虫層の厚みを６０μｍとし、２つの保護層の厚みを共に７０μｍとした。これら以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、実施例５の防虫シートとした。 (Example 5)
A mixture having a different permethrin content from the mixture used in Example 1 was used. The thickness of the insect-proof layer in Example 1 was 60 μm, and the thicknesses of the two protective layers were both 70 μm. Other than these conditions, a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1. An insect repellent sheet was obtained. The content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 5.
　　（実施例６）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。実施例１における防虫層の厚みを４０μｍとし、２つの保護層の厚みを共に８０μｍとした。これら以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、実施例６の防虫シートとした。 (Example 6)
A mixture having a different permethrin content from the mixture used in Example 1 was used. The thickness of the insect-proof layer in Example 1 was 40 μm, and the thickness of the two protective layers was 80 μm. Other than these conditions, a three-layer structure in which an insect repellent layer made of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin was the same as in Example 1. An insect repellent sheet was obtained. The content of permethrin in the obtained insect repellent sheet was 1% by mass. This insect repellent sheet was used as the insect repellent sheet of Example 6.
　　（実施例７）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。これ以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、３質量％であった。この防虫シートを、実施例７の防虫シートとした。 (Example 7)
A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 3 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 7.
　　（実施例８）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。これ以外の条件は、実施例１と同様の条件により、０．１％ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、０．１質量％であった。この防虫シートを、実施例８の防虫シートとした。 (Example 8)
A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1. The insect-proof layer made of a highly crystalline homopolypropylene resin containing 0.1% permethrin was sandwiched between two protective layers made of a highly crystalline homopolypropylene resin. A three-layer insect-proof sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 0.1 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 8.
　　（実施例９）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。これ以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、５質量％であった。この防虫シートを、実施例９の防虫シートとした。 Example 9
A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 5 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 9.
　　（実施例１０）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。これ以外の条件は、実施例１と同様の条件により、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、０．０１質量％であった。この防虫シートを、実施例１０の防虫シートとした。 (Example 10)
A mixture having a different permethrin content from the mixture used in Example 1 was used. The other conditions were the same as in Example 1, and a three-layer structure in which an insect repellent layer composed of a highly crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers composed of a highly crystalline homopolypropylene resin. An insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 0.01 mass%. This insect repellent sheet was used as the insect repellent sheet of Example 10.
　　（比較例１）
　実施例１で用いたマスターバッチペレットと高結晶性ホモポリプロピレン樹脂からなるペレットを溶融して混合し、ペルメトリンを所定の含有量で含有する混合物を得た。この混合物を共押出Ｔダイ成型装置から押し出し、ペルメトリンを含有する高結晶性ホモポリプロピレン樹脂からなる単層構造の防虫シートを得た。得られた防虫シートの厚みは、２００μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、比較例１の防虫シートとした。 (Comparative Example 1)
The master batch pellet used in Example 1 and the pellet made of the highly crystalline homopolypropylene resin were melted and mixed to obtain a mixture containing permethrin at a predetermined content. This mixture was extruded from a co-extrusion T-die molding apparatus to obtain an insecticidal sheet having a single layer structure made of a highly crystalline homopolypropylene resin containing permethrin. The obtained insect-proof sheet had a thickness of 200 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Comparative Example 1.
　　（比較例２）
　実施例２で用いたマスターバッチペレットと高結晶性ホモポリプロピレン樹脂からなるペレットを溶融して混合し、エトフェンプロックスを所定の含有量で含有する混合物を得た。この混合物を共押出Ｔダイ成型装置から押し出し、エトフェンプロックスを含有する高結晶性ホモポリプロピレン樹脂からなる単層構造の防虫シートを得た。得られた防虫シートの厚みは、２００μｍであった。また、得られた防虫シートに対するエトフェンプロックスの含有量は、１質量％であった。この防虫シートを、比較例２の防虫シートとした。 (Comparative Example 2)
The master batch pellets used in Example 2 and the pellets made of highly crystalline homopolypropylene resin were melted and mixed to obtain a mixture containing etofenprox at a predetermined content. This mixture was extruded from a coextrusion T-die molding apparatus to obtain an insecticidal sheet having a single layer structure made of a highly crystalline homopolypropylene resin containing etofenprox. The obtained insect-proof sheet had a thickness of 200 μm. Moreover, content of etofenprox with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Comparative Example 2.
　　（比較例３）
　高結晶性ホモポリプロピレン樹脂を溶融し、溶融物を得た。溶融物を共押出Ｔダイ成型装置から押し出し、高結晶性ホモポリプロピレン樹脂からなる単層構造のフィルムを得た。得られたフィルムの厚みは、２００μｍであった。このフィルムを、比較例３の防虫シートとした。 (Comparative Example 3)
A highly crystalline homopolypropylene resin was melted to obtain a melt. The melt was extruded from a coextrusion T-die molding apparatus to obtain a film having a single layer structure made of a highly crystalline homopolypropylene resin. The thickness of the obtained film was 200 μm. This film was used as the insect repellent sheet of Comparative Example 3.
　　（比較例４）
　ペルメトリンを含有する低結晶性ランダムポリプロピレン樹脂からなるマスターバッチペレットを用意した。高結晶性ホモポリプロピレン樹脂からなるペレットを用意した。溶融したマスターバッチペレットと低結晶性ランダムポリプロピレン樹脂を混合し、ペルメトリンを所定の含有量で含有する混合物を得た。ペレットを溶融し、溶融物を得た。これらの混合物及び溶融物を、共押出Ｔダイ成型装置から押し出し、ペルメトリンを含有する低結晶性ホモポリプロピレン樹脂からなる防虫層が、高結晶性ホモポリプロピレン樹脂からなる２つの保護層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、防虫層の厚みは、１４４μｍであり、２つの保護層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、比較例４の防虫シートとした。 (Comparative Example 4)
Master batch pellets made of a low crystalline random polypropylene resin containing permethrin were prepared. Pellets made of highly crystalline homopolypropylene resin were prepared. The melted master batch pellet and the low crystalline random polypropylene resin were mixed to obtain a mixture containing permethrin at a predetermined content. The pellet was melted to obtain a melt. These mixtures and melts were extruded from a coextrusion T-die molding apparatus, and an insect repellent layer made of a low crystalline homopolypropylene resin containing permethrin was sandwiched between two protective layers made of a high crystalline homopolypropylene resin 3 A layered insect repellent sheet was obtained. In the obtained insect repellent sheet, the thickness of the insect repellent layer was 144 μm, and the thicknesses of the two protective layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Comparative Example 4.
　　（比較例５）
　実施例１で用いた混合物とはペルメトリンの含有量が異なる混合物を用いた。実施例１において防虫層に用いた材料と保護層に用いた材料を入れ替えた。これら以外の条件は、実施例１と同様の条件により、高結晶性ホモポリプロピレン樹脂からなる中心層が、ペルメトリンを含有する高結晶ホモポリプロピレン樹脂からなる２つの外層によって挟まれた３層構造の防虫シートを得た。得られた防虫シートにおいて、中心層の厚みは、１４４μｍであり、２つの外層の厚みは、共に２８μｍであった。また、得られた防虫シートに対するペルメトリンの含有量は、１質量％であった。この防虫シートを、比較例５の防虫シートとした。 (Comparative Example 5)
A mixture having a different permethrin content from the mixture used in Example 1 was used. In Example 1, the material used for the insect repellent layer and the material used for the protective layer were interchanged. The conditions other than these are the same as those in Example 1, and a three-layer insect repellent in which a central layer made of a highly crystalline homopolypropylene resin is sandwiched between two outer layers made of a highly crystalline homopolypropylene resin containing permethrin. A sheet was obtained. In the obtained insect-proof sheet, the thickness of the central layer was 144 μm, and the thicknesses of the two outer layers were both 28 μm. Moreover, content of permethrin with respect to the obtained insect-proof sheet | seat was 1 mass%. This insect repellent sheet was used as the insect repellent sheet of Comparative Example 5.
　　（結晶化度の測定）
　実施例１～１０および比較例１～５の防虫シートについて、保護層（外層）の母材を構成するポリプロピレン樹脂の結晶化度（比較例１～３については、防虫シートの母材を構成するポリプロピレン樹脂の結晶化度）を粉末Ｘ線回析法により測定した。また、防虫層（中心層）の母材を構成するポリプロピレン樹脂の結晶化度は、防虫層を形成する条件と同様の条件で単層の防虫層（シート）を形成し、この防虫層（シート）の母材を構成するポリプロピレン樹脂の結晶化度を、粉末Ｘ線回折法により測定することにより求めた。結果を表１に示す。 (Measurement of crystallinity)
For the insect repellent sheets of Examples 1 to 10 and Comparative Examples 1 to 5, the degree of crystallinity of the polypropylene resin constituting the base material of the protective layer (outer layer) (for Comparative Examples 1 to 3, the base material of the insect repellent sheet is constituted. The crystallinity of the polypropylene resin) was measured by a powder X-ray diffraction method. The crystallinity of the polypropylene resin constituting the base material of the insect repellent layer (center layer) is such that a single insect repellent layer (sheet) is formed under the same conditions as those for forming the insect repellent layer. The crystallinity of the polypropylene resin constituting the base material was determined by measuring by a powder X-ray diffraction method. The results are shown in Table 1.
　［表１］ 
Figure JPOXMLDOC01-appb-I000001
[Table 1]
Figure JPOXMLDOC01-appb-I000001
　　（評価１：安全性評価）
　本実施形態の防虫シートの安全性を評価するために、以下に示す評価を行った。 (Evaluation 1: Safety evaluation)
In order to evaluate the safety of the insect-proof sheet of this embodiment, the following evaluation was performed.
　実施例１～１０および比較例１～５の防虫シートの片側表面（片側の保護層の表面）を、それぞれアセトンを湿らせた脱脂綿でふき、脱脂綿からアセトンを抽出した。ガスクロマトグラフ質量分析計（GC-MS）を用いて、抽出したアセトンに含まれる防虫剤の量をそれぞれ測定した。測定された防虫剤の量から、防虫シート１ｃｍ２当たりの表面に露出する防虫剤の量（ｎｇ/ｃｍ２）をそれぞれ算出した。算出結果から、各防虫シートの表面（保護層の表面）に露出する防虫剤の量が、ＡＤＩ基づいて算出される体重１５ｋｇの乳幼児の１日当りの許容摂取量となる時の各防虫シートの面積（ｍ２）（以下、「許容摂取量となる時の面積」ともいう。）を算出した。なお、ＡＤＩ基づいて算出される体重１５ｋｇの乳幼児の１日当りの許容摂取量は、防虫剤がペルメトリンである場合、０．７５ｍｇであり、防虫剤がエトフェンプロックスである場合、０．４５ｍｇである。 One side surface (the surface of the protective layer on one side) of the insect repellent sheets of Examples 1 to 10 and Comparative Examples 1 to 5 was respectively wiped with absorbent cotton moistened with acetone, and acetone was extracted from the absorbent cotton. The amount of the insect repellent contained in the extracted acetone was measured using a gas chromatograph mass spectrometer (GC-MS). From the measured amount of insect repellent, the amount of insect repellent (ng / cm 2 ) exposed on the surface per 1 cm 2 of insect repellent sheet was calculated. From the calculation results, the area of each insect repellent sheet when the amount of the insect repellent exposed on the surface of each insect repellent sheet (the surface of the protective layer) is the permissible daily intake of a 15 kg body weight infant calculated based on ADI. (M 2 ) (hereinafter also referred to as “the area when the allowable intake is reached”) was calculated. In addition, the permissible daily intake for an infant weighing 15 kg calculated based on ADI is 0.75 mg when the insect repellent is permethrin, and 0.45 mg when the insect repellent is etofenprox. .
　安全性の評価は、以下の評価基準に従って行った。なお、評価が“Ａ”である場合、優れた安全性を有すると判断し、評価が“Ｂ”である場合、安全性を有すると判断し、評価が“Ｃ”の場合、安全性を有さないと判断した。結果を後述する表２に示す。
［評価基準］
　Ａ：摂取許容量となる時の面積が０．５ｍ２超である。
　Ｂ：摂取許容量となる時の面積が０．１ｍ２以上０．５ｍ２以下である。
　Ｃ：摂取許容量となる時の面積が０．１ｍ２未満である。 Safety was evaluated according to the following evaluation criteria. If the evaluation is “A”, it is judged to have excellent safety. If the evaluation is “B”, it is judged to have safety. If the evaluation is “C”, safety is given. I decided not to. The results are shown in Table 2 described later.
[Evaluation criteria]
A: The area when the intake allowance is more than 0.5 m 2 .
B: The area when it becomes the intake allowance is 0.1 m 2 or more and 0.5 m 2 or less.
C: The area when the intake allowance is less than 0.1 m 2 .
　　（評価２：忌避性評価）
　本実施形態の防虫シートの忌避性能を評価するために、以下に示す評価を行った。 (Evaluation 2: repellent evaluation)
In order to evaluate the repellent performance of the insect-proof sheet of this embodiment, the following evaluation was performed.
　屋外に設置された蛍光灯ダウンライトのカバー（丸型、直径１７ｃｍ）表面を、実施例１～１０および比較例１～５の防虫シートでそれぞれ覆った。ライトを１０分間点灯し、１０分後、各防虫シートで覆われたカバー上に停留していた飛翔性昆虫の頭数を計測した。なお、カバーに停留していた飛翔性昆虫は、全てユスリカであった。 The surface of a fluorescent light downlight cover (round shape, diameter 17 cm) installed outdoors was covered with the insect-proof sheets of Examples 1 to 10 and Comparative Examples 1 to 5, respectively. The light was turned on for 10 minutes, and after 10 minutes, the number of flying insects that had stopped on the cover covered with each insect repellent sheet was measured. All the flying insects that remained on the cover were chironomids.
　防虫剤を含有しない比較例３の防虫シートで覆われたカバー上に停留していた飛翔性昆虫の頭数を基準として、計測された飛翔性昆虫の頭数から、下記式（ａ）に基づき、各防虫シートの忌避率を算出した。
Figure JPOXMLDOC01-appb-I000002
　式（ａ）において、Ｘは、比較例３の防虫シートで覆われたカバー上に停留していた飛翔性昆虫の頭数を示し、Ｙは、各防虫シートで覆われたカバー上に停留していた飛翔性昆虫の頭数を示す。 Based on the number of flying insects measured on the basis of the number of flying insects retained on the cover covered with the insect repellent sheet of Comparative Example 3 containing no insect repellent, based on the following formula (a), The repellent rate of the insect repellent sheet was calculated.
Figure JPOXMLDOC01-appb-I000002
In the formula (a), X represents the number of flying insects that were retained on the cover covered with the insect repellent sheet of Comparative Example 3, and Y was retained on the cover covered with each insect repellent sheet. Indicates the number of flying insects.
　忌避性の評価は、以下の評価基準に従って行った。なお、評価が“Ａ”である場合、優れた忌避性を有すると判断し、評価が“Ｂ”である場合、忌避性を有すると判断し、評価が“Ｃ”の場合、忌避性を有さないと判断した。結果を後述する表２に示す。
［評価基準］
　Ａ：忌避率が６０％を超える
　Ｂ：忌避率が３０～６０％
　Ｃ：忌避率が３０％未満 Evaluation of repellency was performed according to the following evaluation criteria. When the evaluation is “A”, it is determined that the product has excellent repellency. When the evaluation is “B”, it is determined that the device has repellent properties. When the evaluation is “C”, the device has repellent properties. I decided not to. The results are shown in Table 2 described later.
[Evaluation criteria]
A: Repellent rate exceeds 60% B: Repellent rate is 30-60%
C: Repelling rate is less than 30%
　　（評価３：塵埃付着抑制効果の評価）
　本実施形態の防虫シートの塵埃付着抑制効果を評価するために、以下に示す評価を実施した。 (Evaluation 3: Evaluation of dust adhesion suppression effect)
In order to evaluate the dust adhesion suppression effect of the insect-proof sheet of the present embodiment, the following evaluation was performed.
　実施例１～１０および比較例１～５の防虫シートを１０ｃｍ×１０ｃｍに切断し、切断した各防虫シートの上面（保護層）に混合ダストを均等に乗せた。混合ダストが乗った各防虫シートを持ち上げて裏返し、所定回数の振動を与えることにより、防虫シートに付着していない未付着の混合ダストを落下させた。混合ダストを乗せる前の各防虫シートの重量と未付着の混合ダストを落下させた後の各防虫シートの重量を測定し、各防虫シートに付着した混合ダストの重量を算出した。なお、混合ダストは、ＪＩＳ　Ｚ　８９０１に規定される試験用粉体１の１５種を用いた。 The insect repellent sheets of Examples 1 to 10 and Comparative Examples 1 to 5 were cut into 10 cm × 10 cm, and the mixed dust was evenly placed on the upper surface (protective layer) of each cut insect repellent sheet. Each insect repellent sheet carrying the mixed dust was lifted and turned over, and a predetermined number of vibrations were applied to drop unadhered mixed dust not adhering to the insect repellent sheet. The weight of each insect repellent sheet before putting mixed dust and the weight of each insect repellent sheet after dropping unadhered mixed dust were measured, and the weight of the mixed dust adhering to each insect repellent sheet was calculated. As the mixed dust, 15 kinds of test powder 1 defined in JIS Z 8901 were used.
　塵埃付着抑制効果の評価は、以下の評価基準に従って行った。なお、評価が“Good”である場合、塵埃付着抑制効果を有すると判断した。結果を後述する表２に示す。
［評価基準］
　Good：防虫シートに付着した混合ダストの平均重量が６０ｍｇ以下である。
　Poor: 防虫シートに付着した混合ダストの平均重量が６０ｍｇを超える。 The dust adhesion suppression effect was evaluated according to the following evaluation criteria. In addition, when evaluation was "Good", it judged that it had a dust adhesion inhibitory effect. The results are shown in Table 2 described later.
[Evaluation criteria]
Good: The average weight of the mixed dust adhered to the insect-proof sheet is 60 mg or less.
Poor: The average weight of the mixed dust adhering to the insect-proof sheet exceeds 60 mg.
　［表２］
Figure JPOXMLDOC01-appb-I000003
[Table 2]
Figure JPOXMLDOC01-appb-I000003
　表２に示すように、実施例１～１０の防虫シートは、評価１（安全性評価）及び評価２（忌避性評価）の評価結果が“Ａ”又は“Ｂ”であり、評価３（塵埃付着抑制効果の評価）の評価結果が“Good”であった。この結果から、本実施形態の防虫シートが、安全性、忌避性及び塵埃付着抑制効果を有していることが理解できる。より具体的には、本実施形態の防虫シートは、上述した構成とすることにより、防虫シート表面に露出する防虫剤の量を防虫効果を発揮させることができる必要最低限の量に制御することができ、安全性を確保できるとともに、塵埃の付着も抑制できることがわかる。また、実施例１～１０の防虫シートが塵埃付着抑制効果を有していたことから、本実施形態の防虫シートは、防虫効果を持続できるとともに、タック性（粘着性）が生じ難く、成形し易いことも理解できる。 As shown in Table 2, the insect repellent sheets of Examples 1 to 10 have an evaluation result of “A” or “B” in evaluation 1 (safety evaluation) and evaluation 2 (repellency evaluation), and evaluation 3 (dust dust) The evaluation result of the “adhesion suppression effect” was “Good”. From this result, it can be understood that the insect-proof sheet of the present embodiment has safety, repellency, and dust adhesion suppression effects. More specifically, by controlling the insect repellent sheet of this embodiment to the above-described configuration, the amount of the insect repellent exposed on the surface of the insect repellent sheet is controlled to the minimum necessary amount that can exert the insect repellent effect. It is understood that safety can be ensured and adhesion of dust can be suppressed. In addition, since the insect repellent sheets of Examples 1 to 10 had an effect of suppressing dust adhesion, the insect repellent sheet of this embodiment can maintain the insect repellent effect and is difficult to produce tackiness (adhesiveness). I understand that it is easy.
　一方、比較例１～５の防虫シートは、評価１～３の少なくともいずれかの評価において、評価結果が“Poor”又は“Ｃ”となった。この結果から、比較例１～５の防虫シートは、安全性、忌避性、塵埃付着抑制効果の少なくともいずれかを有さないことが理解できる。 On the other hand, the insect-proof sheets of Comparative Examples 1 to 5 were evaluated as “Poor” or “C” in at least one of the evaluations 1 to 3. From this result, it can be understood that the insect repellent sheets of Comparative Examples 1 to 5 do not have at least one of safety, repellency, and dust adhesion suppressing effect.
　特に、比較例１～２及び５の防虫シートは、評価１の評価結果が“Ｃ”となった。この結果から、単層構造の防虫シートや、外層に防虫剤が含有される３層構造の防虫シートでは、防虫シートの表面に防虫剤が露出しやすいことが理解できる。また、比較例１～２及び５の防虫シートは、評価３の評価結果が“Poor”となった。このような結果となった原因の一つとしては、単層構造の防虫シートや、外層に防虫剤が含有される３層構造の防虫シートでは、防虫剤が防虫シートの表面に露出しやすく、塵埃が付着しやすいことが考えられる。 In particular, the insect-proof sheets of Comparative Examples 1 to 2 and 5 have an evaluation result of Evaluation 1 of “C”. From this result, it can be understood that the insect repellent is easily exposed on the surface of the insect repellent sheet in the case of the insect repellent sheet having a single layer structure or the insect repellent sheet having a three layer structure containing the insect repellent in the outer layer. In addition, the insect-proof sheets of Comparative Examples 1-2 and 5 had an evaluation result of Evaluation 3 of “Poor”. As one of the causes that resulted in this, the insect repellent sheet with a single layer structure or the insect repellent sheet with a three layer structure containing an insect repellent in the outer layer, the repellent is easily exposed on the surface of the insect repellent sheet, It is thought that dust is likely to adhere.
　また、比較例４の防虫シートは、評価２の評価結果が“Ｃ”であり、評価１の結果に示されるように、許容摂取量となる時の面積が実施例１～１０の防虫シートよりも広かった。この結果から、保護層を構成する熱可塑性樹脂の結晶化度が防虫層を構成する熱可塑性樹脂の結晶化度よりも大きい防虫シートでは、防虫剤が保護層を移動しにくく、防虫シートの外部に防虫剤を放出しにくいことが理解できる。 In addition, the insect repellent sheet of Comparative Example 4 has an evaluation result of “C” in evaluation 2, and as shown in the result of evaluation 1, the area when the allowable intake is reached is greater than that of the insect repellent sheets of Examples 1 to 10. It was also wide. From this result, in the insect repellent sheet, the crystallization degree of the thermoplastic resin constituting the protective layer is larger than the crystallization degree of the thermoplastic resin constituting the insect repellent layer, it is difficult for the insect repellent to move through the protective layer. It can be understood that it is difficult to release the insect repellent.
　なお、比較例３の防虫シートは、評価３において、付着する混合ダストの量が最も少ないが、これは、防虫シートに防虫剤が含まれていないことが原因であると考えられる。 In addition, the insect repellent sheet of Comparative Example 3 has the smallest amount of adhering mixed dust in Evaluation 3, which is considered to be caused by the fact that the insect repellent sheet does not contain an insect repellent.
　また、防虫シートに対する防虫剤の含有量が０．１質量％以上である実施例１～９の防虫シートは、防虫剤の含有量が０．１質量％未満（０．０１質量％）である実施例１０の防虫シートと比較し、忌避率が１１％以上も向上した。この結果から、防虫剤の含有量が０．１質量％以上である防虫シートは、防虫剤の含有量が０．１質量％未満である防虫シートと比較し、防虫効果をさらに発揮しやすいことが理解できる。 In addition, the insect repellent sheets of Examples 1 to 9 having an insect repellent content of 0.1% by mass or more with respect to the insect repellent sheet have an insect repellent content of less than 0.1% by mass (0.01% by mass). Compared with the insect repellent sheet of Example 10, the repelling rate was improved by 11% or more. From this result, the insect repellent sheet having an insect repellent content of 0.1% by mass or more is more likely to exert the insect repellent effect as compared with the insect repellent sheet having an insect repellent content of less than 0.1% by mass. Can understand.
１：防虫シート
２：防虫層
３：保護層
４：防虫剤 1: insect repellent sheet 2: insect repellent layer 3: protective layer 4: insect repellent

Claims (5)

  1. 　防虫剤を放出可能である防虫シートであって、
    　前記防虫剤を含有し、熱可塑性樹脂からなる防虫層と、
    　前記防虫層の外面と接触して前記防虫層を挟む、熱可塑性樹脂からなる２つの保護層と、を有し、
    　前記保護層を構成する熱可塑性樹脂の結晶化度が、前記防虫層を構成する熱可塑性樹脂の結晶化度以下であることを特徴とする防虫シート。     An insect repellent sheet capable of releasing an insect repellent,
    An insect repellent layer containing the insect repellent and made of a thermoplastic resin;
    Two protective layers made of a thermoplastic resin that are in contact with the outer surface of the insect repellent layer and sandwich the insect repellent layer;
    The insect repellent sheet, wherein the crystallinity of the thermoplastic resin constituting the protective layer is equal to or less than the crystallinity of the thermoplastic resin constituting the insect repellent layer.
  2. 　前記防虫剤の主成分がピレスロイド系防虫剤であることを特徴とする請求項１に記載の防虫シート。 The insect repellent sheet according to claim 1, wherein a main component of the insect repellent is a pyrethroid insect repellent.
  3. 　前記ピレスロイド系防虫剤がペルメトリンまたはエトフェンプロックスの少なくとも１種類以上であることを特徴とする請求項２に記載の防虫シート。 The insect repellent sheet according to claim 2, wherein the pyrethroid insect repellent is at least one of permethrin or etofenprox.
  4. 　前記各保護層の厚さが１μｍ以上、１００μｍ以下であることを特徴とする請求項１から３のいずれか一つに記載の防虫シート。 The insect-proof sheet according to any one of claims 1 to 3, wherein the thickness of each protective layer is 1 µm or more and 100 µm or less.
  5. 　前記防虫シートに対する前記防虫剤の含有量が０．１質量％以上、５質量％以下であることを特徴とする請求項１から４のいずれか一つに記載の防虫シート。 The insect repellent sheet according to any one of claims 1 to 4, wherein a content of the insect repellent with respect to the insect repellent sheet is 0.1 mass% or more and 5 mass% or less.
PCT/JP2016/057318 2015-03-09 2016-03-09 Insect repellent sheet WO2016143810A1 (en)

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JP2019172623A (en) * 2018-03-29 2019-10-10 平岡織染株式会社 Sheet excellent in sustainability of insect-proofing effect
JP2020109070A (en) * 2018-12-28 2020-07-16 広島化成株式会社 Partitioning sheet
CN116369300A (en) * 2022-12-19 2023-07-04 佛山欧神诺陶瓷有限公司 Cockroach-preventing light ceramic plate capable of being slowly released for long time and preparation method thereof
US11825837B2 (en) 2019-06-04 2023-11-28 S. C. Johnson & Son, Inc. Dispenser and method of use thereof

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JP2005515766A (en) * 2002-01-31 2005-06-02 ベステルガールド フランドセン アクティーゼルスカブ Laminated insecticide dispenser
JP2011529926A (en) * 2008-08-06 2011-12-15 ベステルガールド フランドセン ソシエテ アノニム Insecticide polymer matrix comprising HDPE and LDPE

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JP2005515766A (en) * 2002-01-31 2005-06-02 ベステルガールド フランドセン アクティーゼルスカブ Laminated insecticide dispenser
JP2011529926A (en) * 2008-08-06 2011-12-15 ベステルガールド フランドセン ソシエテ アノニム Insecticide polymer matrix comprising HDPE and LDPE

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019172623A (en) * 2018-03-29 2019-10-10 平岡織染株式会社 Sheet excellent in sustainability of insect-proofing effect
JP2020109070A (en) * 2018-12-28 2020-07-16 広島化成株式会社 Partitioning sheet
JP7282369B2 (en) 2018-12-28 2023-05-29 広島化成株式会社 Insect repellent partition sheet
US11825837B2 (en) 2019-06-04 2023-11-28 S. C. Johnson & Son, Inc. Dispenser and method of use thereof
CN116369300A (en) * 2022-12-19 2023-07-04 佛山欧神诺陶瓷有限公司 Cockroach-preventing light ceramic plate capable of being slowly released for long time and preparation method thereof

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