Adhesive strips containing pesticides

Abstract

This invention relates to an adhesive tape 10 containing pesticide, comprising a substrate 11 and an adhesive layer 12 disposed on the substrate 11. The adhesive layer 12 contains an emulsion adhesive and a penetrating and migrating pesticide. The emulsion adhesive is preferably an acrylic emulsion adhesive or a rubber-based emulsion adhesive with latex rubber as the main component. The pesticide is preferably at least one of an insecticide, fungicide, insecticide-fungicide combination, herbicide, and plant growth regulator.

Description

Technical Field

[0001] This invention relates to an adhesive tape containing pesticides. Prior Technology

[0002] Currently, pesticides are safely managed through application methods tailored to the type of pesticide or the target organism. However, methods such as aerial spraying often involve uniform treatment of the entire field. While this method offers advantages like low operating costs and the ability to treat fields uniformly, it cannot prevent workers from being exposed to drifting pesticides, and its impact on the surrounding environment and ecosystem is highly controversial. Furthermore, although uniform treatment is possible, some pesticides applied to the target area adhere to the target organism, while others do not, falling into the soil and failing to exert their effect; in terms of efficacy, this method is essentially ineffective.

[0003] On the other hand, depending on the treatment method, there are also methods such as trunk injection or coating. However, trunk injection requires drilling holes in each target object for treatment, which is not only time-consuming and labor-intensive, but may also affect the growth of the target object. Furthermore, although coating is simpler than trunk injection, since it only involves coating, the surface of the liquid is not protected, and there is a risk that it may leak into the soil due to wind and rain, thus failing to achieve the desired effect, or there is a concern that the liquid may drift to surrounding plants.

[0004] Therefore, as a processing method different from the above-mentioned methods, Patent Document 1 proposes a weeding sheet in which a mixture of herbicide picroxene, which is active like indoleacetic acid, and lanolin is applied to the adhesive layer of the rubber sheet and then coated onto the substrate. Furthermore, Patent Document 2 proposes an agricultural and horticultural disease control sheet that is a mixture of an acrylic adhesive and an agricultural and horticultural fungicide. Furthermore, Patent Document 2 discloses an agricultural and horticultural disease control sheet, which has a substrate and an agricultural and horticultural disease control composition layer including an adhesive layer, and the material of the adhesive layer is described as an acrylic adhesive. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 49-99725 [Patent Document 2] Japanese Patent Publication No. 7-23282 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] However, the pesticide described in Patent Document 1 requires a large amount of pesticide per 1 cm² sheet, and a large amount of pesticide is needed to kill the target plant. Furthermore, Patent Document 2 lists non-penetrating fungicides such as tetrachloroisobenzonitrile and zinc manganese nitrile as fungicides. Therefore, it is only effective on the parts that need to be protected, such as the area near the graft, the grafting point, or the cut, and it is unclear whether it has a medicinal effect on the entire plant. The present invention was made in view of the above circumstances, and its purpose is to provide a pesticide-containing adhesive tape that can efficiently apply pesticides to target plants. [Technical means to solve the problem]

[0008] The inventors conducted intensive research and discovered that by using an emulsion-based adhesive as the material for pesticide-containing adhesives, the pesticide dispersed in the adhesive is absorbed by the plant through water transpired by the plant. Therefore, the pesticide exhibits excellent permeability to the target plant, enabling efficient application of the pesticide to the target plant. Furthermore, the inventors also discovered that, even with the same composition, an emulsion-type adhesive, as a coagulated aggregate of adhesive microparticles, has a larger surface area and more opportunities for contact with water compared to an adhesive dissolved in a solvent and then coated. Therefore, it can more efficiently apply the pesticide to the plant, thus completing this invention.

[0009] That is, the present invention is a pesticide-containing adhesive tape, which has a substrate and a pesticide-containing adhesive layer disposed on the substrate, the adhesive layer containing an emulsion adhesive and a pesticide with penetrating and migrating properties.

[0010] Acrylic emulsion adhesives are preferred among emulsion adhesives.

[0011] Emulsion adhesives can be rubber-based emulsion adhesives with latex rubber as the main component.

[0012] Pesticides are preferably at least one of insecticides, fungicides, insecticide-fungicides, herbicides, and plant growth regulators.

[0013] The acrylic emulsion adhesive is preferably formed by polymerizing a mixture of monomers containing the following components: (a) alkyl methacrylates with 4 to 12 alkyl carbons, (b) a carboxyl-containing monomer, and (c) a copolymerizable monomer, wherein the content of (a) alkyl methacrylates with 4 to 12 alkyl carbons is 50% to 99.5% by mass, the content of (b) the carboxyl-containing monomer is 0.5% to 10% by mass, and the content of (c) the copolymerizable monomer is 0% to 40% by mass.

[0014] The rubber-based emulsion adhesive contains latex rubber and an adhesive agent. The latex rubber is at least one of natural rubber, chloroprene rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and ethylene-vinyl acetate copolymer. The latex rubber content is preferably 30% to 80% by mass relative to 100% by mass of the rubber-based emulsion adhesive. [Effects of the Invention]

[0015] According to the pesticide-containing adhesive tape of the present invention, pesticides can be applied to target plants with high efficiency. Simple Explanation of the Diagram

[0016] Figure 1 is a cross-sectional view showing one embodiment of the pesticide-containing adhesive tape of the present invention. Figure 2 is a photograph of the camellia before the experiment in Example 4. Figure 3 is a photograph of the camellia after the experiment in Example 4. Figure 4 is a photograph of the kudzu vine before the experiment in Example 7. Figure 5 is a photograph of the kudzu after the experiment in Example 7. Implementation

[0017] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. These embodiments are for illustrative purposes only, and the present invention is not limited to any of the embodiments shown below.

[0018] [Adhesive strip containing pesticides] The embodiments of the present invention will be described with reference to FIG1. As shown in Figure 1, the pesticide-containing adhesive tape 10 of the present invention comprises a substrate 11 and a pesticide-containing adhesive layer 12 disposed on the substrate. The following is a detailed explanation of the components of pesticide-containing adhesive tape.

[0019] (Substrate) The pesticide-containing adhesive tape 10 of the present invention is used to attach or wrap around the trunk or stem of a tree. Therefore, the substrate 11 is preferably flexible or soft and has the physical properties of being able to adhere closely to the trunk or stem and preventing pesticide evaporation and leakage. For example, the following materials may be used: polyolefin materials such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; acrylic materials such as polyvinyl alcohol and polymethyl methacrylate; polyester materials such as polyethylene terephthalate, polybutylene terephthalate, and polycarbonate; polyamide materials such as nylon 6 and nylon 6,6; various ionic polymer materials containing zinc, sodium, or other metal ions in their structure; styrene materials such as polystyrene, styrene-isoprene copolymer, and styrene-butadiene copolymer; polyurethane materials; vinyl chloride materials; fluorine materials such as tetrafluoroethylene, tetrafluoropropylene, polyvinylidene fluoride, tetrafluoroethylene-ethylene copolymer resin, polyvinyl chloride trifluoroethylene, and polyfluorinated vinylidene; cellulose materials such as acetic acid and cellulosic; biodegradable plastics such as polylactic acid; metal foils such as aluminum, silver, and gold; and mixtures or laminates of one or more of the above materials.

[0020] The thickness of the substrate 11 can be appropriately selected considering physical properties such as ductility, tensile strength, workability, and its ability to follow the surface of the trunk or stem. Preferably, it is between 5 μm and 200 μm, and more preferably between 20 μm and 100 μm. If the thickness of the substrate 11 is less than 5 μm, the strength and workability of the pesticide-containing adhesive tape 10 will decrease, making it difficult to adhere to the trunk or stem, and it may sometimes crack due to contact with the bark. Furthermore, if the thickness of the substrate 11 exceeds 200 μm, the pesticide-containing adhesive tape 10 will have difficulty following the trunk or stem when wrapped around it, and it will easily peel off. When the substrate 11 is a metal foil, its thickness is preferably 5 μm or more and 200 μm or less, and more preferably 20 μm or more and 100 μm or less. Furthermore, when the substrate 11 is a resin film, its thickness is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 200 μm or less, and even more preferably 10 μm or more and 100 μm or less.

[0021] Furthermore, when the thickness of the substrate 11 is extremely thin, the following carrier film may be provided on the side opposite to the side where the adhesive layer 12 is provided (also referred to as one side).

[0022] The size of the substrate 11 can be appropriately selected according to the size of the target plant and the concentration of the herbicide.

[0023] Furthermore, when the substrate 11 is a resin film, at least one of the adhesive layer 12 and the substrate 11 may be subjected to treatments such as sandblasting or corona treatment.

[0024] As the carrier film, known materials can be used, and preferably, various films containing various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomers, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, thermoplastic polyester, and polytetrafluoroethylene can be used to form the carrier film. Furthermore, various films can also be used in a laminated state on paper. Ideally, the carrier membrane formed from these various membranes should be relatively thick or contain materials with high toughness. The thickness of the carrier membrane can be appropriately set, usually above 10 μm, preferably above 20 μm, and its upper limit is about 500 μm.

[0025] The substrate 11 may also contain antioxidants such as phenols or amines, ultraviolet absorbers such as benzophenones, hindered amine light stabilizers, fillers such as calcium carbonate or silicon dioxide, within a range that does not impair the effects of the present invention. The substrate 11 may also be treated as needed by printing coloring, text, etc., applying release agents, primers, weather-resistant treatment agents, etc., or by vapor deposition.

[0026] (Adhesive layer) The adhesive layer 12 contains an emulsion adhesive formed by dispersing an adhesive in water and a penetrating and migrating pesticide. The term "emulsion adhesive" refers to an emulsion in which a non-water-soluble adhesive (adhesive polymer compound) is dispersed in a water-based solvent in the form of microparticles. Examples of non-water-soluble adhesives include: acrylic adhesives, rubber adhesives, silicone adhesives, vinyl alkyl ether adhesives, polyester adhesives, polyamide adhesives, carbamate adhesives, fluorinated adhesives, epoxy adhesives, latex, and other adhesives containing synthetic resins. Methods for producing emulsion adhesives include: methods of emulsifying and polymerizing the monomers of the adhesive (adhesive polymer compound), and methods using a pre-emulsified polymer as the main component. Regarding the former, emulsification and polymerization, the monomer, emulsifier (surfactant), and polymerization initiator are mixed in an aqueous solvent to carry out the polymerization reaction, thereby obtaining a water-dispersible polymer (emulsion).

[0027] Rubber-based emulsion adhesives using latex rubber are those containing emulsified latex rubber and emulsified adhesive additives. Examples of latex rubber include: natural rubber, chloroprene rubber, SBR (styrene-butadiene rubber), butadiene rubber, NBR (acrylonitrile-butadiene rubber), MBR (methyl methacrylate-butadiene rubber), EVA (ethylene-vinyl acetate copolymer), etc. Examples of adhesive additives include: rosin-based resins, terpene resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, benzofuran resins, copolymers of these, modifiers, hydrides, etc. The latex rubber content is preferably 30% to 80% by mass relative to 100% by mass of the rubber-based emulsion adhesive.

[0028] Acrylic emulsion adhesives can be manufactured, for example, by emulsifying and polymerizing two or more acrylic polymeric compounds to obtain copolymers. More specifically, acrylic emulsion adhesives can be manufactured by polymerizing a mixture of monomers containing the following components: (a) alkyl (meth)acrylates with an alkyl group having 4 to 12 carbon atoms, (b) a carboxyl-containing monomer, and (c) a copolymerizable monomer.

[0029] Examples of (a) alkyl acrylates having 4 to 12 alkyl carbons include: (a) butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, lauryl methacrylate, isodecanyl acrylate, etc.

[0030] Examples of (b) carboxyl-containing monomers include: (meth)acrylic acid, butenoic acid, fumaric acid, icosinic acid, maleic acid, citralic acid, 2-carboxyethyl methacrylate, etc.

[0031] Examples of monomers that can be copolymerized (c) include: methyl methacrylate, ethyl acrylate, 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, tridecyl acrylate, tridecyl methacrylate, cyclohexyl acrylate, isoborneol acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, vinyl alcohol, allyl alcohol, acrylamide, N,N-Dimethyl (meth)acrylamide, N-Butyl (meth)acrylamide, N-Hydroxymethyl (meth)acrylamide, N-Hydroxymethylpropane (meth)acrylamide, N-Methoxymethyl (meth)acrylamide, N-Butoxymethyl (meth)acrylamide, (meth)acrylate monomers containing secondary amino groups, (meth)acrylate monomers containing tertiary amino groups, N-substituted (meth)acrylamide monomers containing tertiary amino groups with tertiary amino substituents bonded to the nitrogen atom forming the amino group, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, allyl glycidyl ether, acrylonitrile, methyl methacrylate Nitriles, diacetone (meth)acrylamide, acetone (meth)acrylic acid, vinyl methyl ketone, vinyl ethyl ketone, allyl acetate, vinyl acetate, styrene, acetoethyl methacrylate, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperidone, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylimidazolium, N-vinylpyrrolidone, N-vinylcaprolactone, N-(meth)acrylamide, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-acryloxypropyl Triethoxysilane, 3-(meth)propenyloxypropylmethyldimethoxysilane, 3-(meth)propenyloxypropylmethyldiethoxysilane, 2-(acetylacetoxy)ethyl(meth)acrylate, 2-(meth)propenyloxyethyltrimethoxysilane, 2-(meth)propenyloxyethyltriethoxysilane, γ-(meth)propenyloxypropyltrichlorosilane, γ-(meth)propenyloxypropylmethyldichlorosilane, γ-(meth)propenyloxypropyldimethylchlorosilane, γ-(meth)propenyloxypropyltripropoxysilane, γ-(meth)propenyloxypropylmethyldipropoxysilane, γ- (Meth)propenoxypropyltributoxysilane, (Meth)propenoxypentyltrimethoxysilane, (Meth)propenoxyhexyltrimethoxysilane, (Meth)propenoxyhexyltriethoxysilane, (Meth)propenoxyoctyltrimethoxysilane, (Meth)propenoxydecyltrimethoxysilane, (Meth)propenoxydodecyltrimethoxysilane, (Meth)propenoxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, etc.

[0032] Relative to 100% by mass of the monomer mixture, (a) the content of alkyl methacrylates with 4 to 12 alkyl carbons is preferably 50% to 99.5% by mass, (b) the content of carboxyl-containing monomers is preferably 0.5% to 10% by mass, and (c) the content of copolymerizable monomers is preferably 0% to 40% by mass.

[0033] From the perspective of balancing cohesiveness and adhesion, the content of copolymer in the adhesive layer is preferably 40% by mass or more and 97% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. Furthermore, from the viewpoint of ensuring adhesion to the trunk or stem of the tree, the average particle size of the copolymer particles is preferably 30 nm to 1000 nm, and more preferably 100 nm to 400 nm.

[0034] Adhesives such as rosin resins, terpene resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, benzofuran resins, copolymers, modifiers, and hydrides may also be added to acrylic emulsion adhesives as needed.

[0035] The thickness of the adhesive layer 12 is preferably 10 μm or more and 300 μm or less, and more preferably 15 μm or more and 150 μm or less.

[0036] Regarding the adhesive strength of the adhesive layer, considering the need for long-term close contact with the leaves or stems of plants with uneven surfaces, and the adhesion of the adhesive layer to the back of the substrate, the adhesion strength to BA-SUS (Bright Annealed-Steel Use Stainless) is preferably 0.5 N / 10 mm or more, and more preferably 1.0 N / 10 mm or more.

[0037] The adhesive layer 12 can be configured as a single adhesive layer or as a composite of multiple adhesive layers. When the adhesive layer 12 is configured as a composite of multiple adhesive layers, it can be configured as a composite of different types of adhesive layers.

[0038] The adhesive layer 12 may also contain any of the following additives that are typically formulated in adhesive layers as any component: liquid rubber, crosslinking agent, softener (plasticizer), pH adjuster, antioxidant (antioxidant, preservative), filler, ultraviolet absorber, light stabilizer, colorant, surfactant, and tackifier.

[0039] (pesticide) There are no particular limitations on pesticides, as long as they have penetrating and migratory properties and are effective against plants and pests. However, given their impact not only on plants but also on the environment and other flora and fauna, it is preferable to use pesticides that have obtained pesticide registration. According to the Pesticide Management Act, "pesticides" refer to "fungicides, insecticides, and other agents (including those used as raw materials or materials for the control of bacteria, nematodes, mites, insects, rodents, other animals and plants, or viruses (hereinafter collectively referred to as 'diseases and pests') that harm crops (including trees and agricultural and forestry products, hereinafter referred to as 'crops, etc.')" and "plant growth regulators, germination inhibitors, and other agents used to enhance or inhibit the physiological functions of crops, etc." Furthermore, it stipulates that "natural enemies used to control diseases and pests of crops, etc." are also considered pesticides. Specifically, pesticides can be categorized as follows: insecticides (pesticides for controlling pests that harm crops), fungicides (pesticides for controlling diseases that harm crops), insecticides and fungicides (pesticides that simultaneously control both pests and diseases of crops), herbicides (pesticides for controlling weeds), rodenticides (pesticides for controlling field mice and other pests that harm crops), plant growth regulators (pesticides that promote or inhibit crop growth), attractants (pesticides that primarily use odors to attract pests), spreading agents (pesticides that are mixed with other pesticides to improve the adhesion of the pesticide), natural enemies (natural enemies of pests that harm crops), and microbial agents (pesticides that use microorganisms to control pests and diseases that harm crops). Among these, insecticides, fungicides, insecticides and fungicides, herbicides, and plant growth regulators that possess penetrating and migrating properties can be used in this invention.

[0040] Regarding the dosage of pesticides, the appropriate dosage needs to be adjusted according to the plant species. For example, considering the impact on plants, the preferred dosage relative to 1 cm² of bark is 0.0002 mg / cm² or higher but not exceeding 10 mg / cm², and more preferably 0.0006 mg / cm² or higher but not exceeding 5.0 mg / cm². It is preferable to adjust the concentration and dosage in a manner consistent with this herbicide dosage.

[0041] (Peel off the paper) The pesticide-containing adhesive tape 10 of the present invention can also have a release paper attached to the surface of the adhesive layer. For example, the release paper can be made of plastic films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, unstretched polypropylene, stretched polypropylene, polyethylene, polyurethane, polyvinyl chloride, and polystyrene; processed sheets on which the above-mentioned plastic films have undergone a demolding treatment; paper; laminated paper on which polyethylene or polypropylene plastic films or processed sheets on which such films have undergone a demolding treatment; colorless or colored sheets such as laminated films or sheets formed by stacking such films or sheets together. There is no particular limitation on the thickness of the release paper, but it is preferably 10 μm to 500 μm, more preferably 20 μm to 300 μm, and even more preferably 40 μm to 200 μm.

[0042] Furthermore, from the viewpoint of the preservation stability of the product, the pesticide-containing adhesive tape 10 of the present invention can also be sealed in a bag.

[0043] The pesticide-containing adhesive tape 10 of the present invention can be obtained by mixing an emulsion-based adhesive constituting the adhesive layer 12 with a pesticide to prepare an adhesive layer composition, applying the composition to a substrate 11 and drying it to obtain the adhesive tape 10. An additive may be mixed into the adhesive layer used in this embodiment to promote the stability of the pesticide in the adhesive layer and the penetration of the pesticide during application.

[0044] The pesticide concentration in the adhesive layer is preferably 0.01% to 30% by mass, more preferably 0.1% to 25% by mass, and even more preferably 1% to 20% by mass, relative to 100% by mass of the adhesive composition. Furthermore, considering the penetrability and migration of pesticides, the coating amount of the adhesive layer 12 is preferably 10 g / m2 to 300 g / m2, and more preferably 15 g / m2 to 150 g / m2.

[0045] [Instructions for using adhesive tape containing pesticides] The pesticide-containing adhesive tape 10 of the present invention is attached or wrapped in such a way that the adhesive layer 12 is in close contact with the stem or trunk and leaves of plants or trees, and is left for a required number of days before the effect is apparent. There are no particular restrictions on the location where the pesticide-containing adhesive tape 10 is attached or wrapped around the stem or trunk; it can be selected appropriately.

[0046] The pesticide-containing adhesive tape of the present invention simply attaches or wraps an adhesive sheet containing pesticide to a trunk or stem, thus eliminating the trouble of dilution and spraying, and can only show the effect on the attached plant. Furthermore, the pesticide-containing adhesive tape of the present invention can work efficiently with a small amount compared to pesticide solutions of the same concentration used in previous spraying methods, thus inhibiting soil pollution, drift to the surrounding area, and exposure of workers. Furthermore, the pesticide-containing adhesive tape of the present invention uses an emulsion-based adhesive as the adhesive, thereby sealing the part of the plant stem or leaf to which it is attached, preventing the water released by the plant from escaping into the atmosphere, thus increasing the humidity between the adhesive layer and the plant. It is presumed that this moisture (humidity) allows the pesticide in the adhesive to be efficiently released and penetrate into the plant. That is, even with the same composition, the pesticide-containing adhesive tape of the present invention, being an emulsion type consisting of adhesive microparticle aggregates, has a larger surface area compared to an adhesive dissolved in a solvent and then coated, thus increasing the opportunity for contact with moisture and allowing for more efficient application of pesticides to the plant.

[0047] In particular, when pesticides are added to the adhesive layer to achieve both adhesive and pesticide effects, the required amount of pesticide cannot always be added due to the compatibility between the pesticide and the materials constituting the adhesive layer. However, thanks to advancements in pesticide technology in recent years, even small amounts can be effective in suppressing soil pollution, drift into the surrounding environment, and exposure of workers. [Example]

[0048] The embodiments of the present invention will be described below. The substrate, adhesive layer material, target plants, and pesticides (herbicides) used in the examples and comparative examples are shown below. (1) Substrate: • PET (Polyethylene terephthalate, 25 μm thick) • Cellulose (Cellulfan, 35 μm thickness) (2) Adhesive layer: (2-1) Acrylic emulsion adhesives • Acrylic emulsion adhesive I (2-ethylhexyl acrylate (2-EHA) based) • Acrylic emulsion adhesive II (n-butyl acrylate (BA) based) (2-2) Rubber-based emulsion adhesives • Rubber-based emulsion adhesive I {a mixture of latex rubber (chloroprene rubber, trade name "SKYPRENE (registered trademark) GFL890", manufactured by Tosoh Co., Ltd.) and rosin ester-based adhesive additive (trade name "AQUATAC XR-4343", manufactured by KRATON)} • Rubber-based emulsion adhesive II {A mixture of latex rubber (chloroprene rubber, trade name "SHOPRENE (registered trademark) 654, manufactured by Showa Denko Co., Ltd.) and rosin ester-based adhesive additive (trade name "SUPER ESTER E720", manufactured by Arakawa Chemical Co., Ltd.)} (2-3) Hot melt adhesives A mixture of styrene-isoprene-styrene (SIS, trade name "QUINTAC 3421", manufactured by Zeon Corporation, Japan) and rosin ester-based adhesive (trade name "SUPER ESTER A115", manufactured by Arakawa Chemical Industry Co., Ltd.) A mixture of styrene-isoprene-styrene (SIS, trade name "QUINTAC 3421", manufactured by Zeon Corporation, Japan) and terpene-phenolic adhesive (trade name "YS POLYSTER T115", manufactured by Yasuhara Chemical Co., Ltd.) • Acrylic adhesive (hot melt type, solvent-free, trade name "POLYTHICK AH-300", manufactured by Sanyo Chemical Industry Co., Ltd.) • Naphthenic oil (trade name "SUNPURE NX90", manufactured by Japan Sun Oil Co., Ltd.) (3) Target plants: Camellia, kudzu (4) Pesticides: (4-1) Herbicides • Emethrower (ALS inhibitor) • Galactosyl (EPSP synthase inhibitor) (4-2) Insecticides Dartnam (neonicotinic acid insecticide)

[0049] [Example 1] First, a herbicide is mixed into an acrylic emulsion adhesive I (2-EHA system) to achieve a pesticide concentration of 5% by mass, thus adjusting the adhesive layer composition. This adhesive layer composition is then applied to a substrate and dried to produce an adhesive tape containing pesticide with an adhesive coating amount of 30 g / m².

[0050] [Example 2] Except for using acrylic emulsion adhesive II (BA series) as an adhesive, pesticide-containing adhesive tape was prepared in the same manner as in Example 1.

[0051] [Example 3] A rubber-based emulsion adhesive I was mixed with a herbicide to prepare an adhesive layer composition with a pesticide concentration of 1% by mass. This adhesive layer composition was then applied to a substrate and dried to produce an adhesive tape containing pesticide with an adhesive coating amount of 30 g / m².

[0052] [Comparative Example 1] Using LABO PLASTOMILL (registered trademark) manufactured by Toyo Seiki Co., Ltd., adhesive layer materials (SIS, rosin ester resin, and naphthenic oil) were melt-mixed, and pesticides were added to prepare an adhesive layer composition with a pesticide concentration of 7% by mass. This adhesive layer composition was then coated onto a substrate to produce a pesticide-containing adhesive tape with an adhesive coating amount of 150 g / m².

[0053] [Comparative Example 2] Using LABO PLASTOMILL (registered trademark) manufactured by Toyo Seiki Co., Ltd., adhesive layer materials (SIS, terpene resin, and naphthenic oil) were melt-mixed, and pesticides were added to prepare an adhesive layer composition with a pesticide concentration of 7% by mass. This adhesive layer composition was then coated onto a substrate to produce a pesticide-containing adhesive tape with an adhesive coating amount of 150 g / m².

[0054] [Comparative Example 3] Using LABO PLASTOMILL (registered trademark) manufactured by Toyo Seiki Co., Ltd., an acrylic adhesive (POLYTHICK AH-300) (hot melt type) was mixed with pesticide to prepare an adhesive layer composition with a pesticide concentration of 7% by mass. This adhesive layer composition was then coated onto a substrate to produce an adhesive tape containing pesticide with an adhesive coating amount of 150 g / m².

[0055] For Examples 1-3 and Comparative Examples 1-3 above, the ease of release of the pesticide self-adhesive layer was evaluated using the "24h (hour) release rate" method. Furthermore, for Examples 1-3 and Comparative Examples 1-3 above, the adhesive strength of the adhesive layer was measured. The evaluation steps are as follows. The evaluation results are shown in Table 1.

[0056] (24h release rate) Using a silicone-based adhesive, a 1.20 mm ϕ adhesive tape is fixed to the bottom of a 27 mm ϕ brown glass sample vial with the adhesive side facing up. 10 mL of ultrapure water (pH 6.5~7.3) is added, and the water temperature is maintained at around 23°C while stirring with a stirrer at 75~100 rpm. 2. Take 1 mL of test solution at specific time intervals, and add 1 mL of water each time. 3. Sampling times are set at 2 hours, 4 hours, 6 hours, and 24 hours, and the sample solution is analyzed using HPLC (High Performance Liquid Chromatograph). Furthermore, sampling at 2 hours, 4 hours, and 6 hours prior to the 24-hour sampling time will be conducted as needed (the same applies below). 4. Using the standard reagents of ethionamb manufactured by Fujifilm and Kosei Pure Chemical Industries Co., Ltd. as standard reagents, a calibration curve was prepared, and the amount of ethionamb in the sample solution was quantified according to the following conditions. <Analysis Conditions> Mobile phase: H₂O / acetonitrile / phosphoric acid = 80 / 20 / 0.04 vol. Column: TSgel ODS-100z 5 μm 4.6 mm × 25 cm Column temperature: 40℃ Flow rate: 1.0 mL / min Injection volume: 10~40 μL

[0057] (Adhesion) Adhesive tape containing pesticides, which had been placed at 23°C and 50%RH for more than 24 hours, was cut into 10 mm wide and 10 cm long pieces to make test pieces. These test pieces were then attached to BA-SUS (bright annealed stainless steel) plates using the 180-degree peel test according to JIS Z0237 as a reference, and pressed together using a 1 kg pressing roller. After pressing, the test piece was peeled off at a peel angle of 180° and a speed of 300 mm / min, and the force at this point was measured.

[0058] [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 experimental pesticides Yi Mie Cao Substrate PET (25 μm thickness) adhesive emulsion system Hot melt system Acrylic emulsion adhesive I Acrylic emulsion adhesive II Rubber-based emulsion adhesive I SIS / rosin ester adhesive SIS / terpene-based adhesives acrylic adhesives (2-EHA series) (BA Department) (POLYTHICK AH-300) pesticide concentration 5 wt% 5 wt% 1 wt% 7 wt% 7 wt% 7 wt% Adhesive coating amount 30 g / m2 150 g / m2 24h release rate 41.70% 66.50% 44.00% 3.90% 3.00% 8.00% Adhesion N / 10mm 1.1 3.2 1.4 18.9 17.4 15.8

[0059] As shown in Table 1, it can be seen that the release rate of the pesticide-containing adhesive tape of the present invention using emulsion-based adhesive is significantly higher than that of Comparative Examples 1-3 using hot-melt adhesive.

[0060] Secondly, a practical test of the pesticide-containing adhesive tape of the present invention was conducted.

[0061] [Example 4] Using PET (25 μm thick) as the substrate and acrylic emulsion adhesive II (BA series) as the adhesive, an adhesive tape containing pesticide with a pesticide content of 0.9 mg per 1 cm2 was produced by the same method as described above.

[0062] [Example 5] Except that the amount of pesticide per 1 cm2 is set to 0.6 mg, the pesticide-containing adhesive tape is made in the same manner as in Example 4.

[0063] [Example 6] Except that the amount of pesticide per 1 cm2 is set to 0.1 mg, the pesticide-containing adhesive tape is made in the same manner as in Example 4.

[0064] [Comparative Example 4] Comparative Example 4 uses a SIS / rosin ester-based adhesive additive as the adhesive layer. The adhesive layer is prepared by thermally melting SIS, rosin resin, naphthenic oil, and pesticide using LABO PLASTOMILL. This adhesive composition is coated onto a PET substrate (25 μm thick) to produce an adhesive tape containing pesticide.

[0065] [Practical Experiment] Practical experiments were conducted according to the following steps for Examples 4-6 and Comparative Example 4, and the following evaluations were performed before and after the experiments. The evaluation results are shown in Table 2. Furthermore, a photograph of the camellia before the experiment in Example 4 is shown in Figure 2, and a photograph of the camellia after the experiment is shown in Figure 3. 1. Wrap the pesticide-containing adhesive tape of Examples 4-6 and Comparative Example 4 around a portion of the soil surface of the camellia about 2-3 cm away. 2. To prevent the adhesive and pesticides from deteriorating due to light, cover the surface of the pesticide-containing adhesive tape with aluminum foil. 3. Trial period: June 16, 2019 to September 5, 2019

[0066] (Growth rate (height)%) The height of the camellia was measured before and after the experiment, and the growth rate (height) was calculated according to the following formula. (Tree height after the experiment - Tree height before the experiment) / Tree height before the experiment × 100

[0067] (Growth rate (tree diameter)%) The maximum diameter of the camellia stem at a distance of 2-3 cm from the ground was measured before and after the experiment, and the growth rate (tree diameter) was calculated according to the following formula. (Maximum diameter of trees after the experiment - Maximum diameter of trees before the experiment) / Maximum diameter of trees before the experiment × 100

[0068] (Sprout) Confirm whether the camellia has any new buds and evaluate it according to the following criteria. A: No new buds B: There are signs of new buds sprouting. C: New buds (leaves) sprout.

[0069] (State of a withered leaf) Observe the condition of the camellia leaves and evaluate them according to the following criteria. A: More than 80% of the leaves on the entire tree have changed color. B: More than 50% but less than 80% of the leaves on the entire tree have changed color. C: Less than 50% of the leaves on the entire tree have changed color.

[0070] (Leaf loss rate (%)) The leaf fall rate is calculated using the following formula. (Number of leaves before the experiment - Number of leaves after the experiment) / Number of leaves before the experiment × 100

[0071] [Table 2] Example 4 Example 5 Example 6 Comparative Example 4 adhesive emulsion system Hot melt system Acrylic emulsion adhesive II (BA series) SIS / rosin ester adhesive Object Tree Camellia Substrate PET (25 μm) medicine Yi Mie Cao Adhesive coating amount 150 g / m2 Adhesion area 22.5 cm² (3 pieces of 1.5 x 5 cm each) pesticide concentration 6 wt% 4 wt% 0.68 wt% 4 wt% pesticide dosage 20.25 mg 13.5 mg 2.25 mg 13.5 mg per 1 cm2 0.9 mg 0.6 mg 0.1 mg 0.6 mg 24h release rate 58% 55% 63% 5% leaf fall rate 100% 100% 74.20% 56.00% Number of tablets (before → after the experiment) 55→0 32→0 31→8 75→33 Growth rate (height) -7% -6% -4% -6% Growth rate (tree diameter) 7% 3% 10% 4% sprouts A A A A The state of the withered leaves (discoloration) No remaining leaves No remaining leaves B A Adhesion N / 10 mm 9.7 8.4 6.7 17.2

[0072] As shown in Table 2, Examples 4, 5, and 6, which use emulsion-based adhesives, are more efficient at causing trees to die or inhibiting their growth than Comparative Example 4, which uses a hot-melt rubber-based adhesive. The reason for this is presumably that the emulsion-based adhesive retains the water released by the plant between the adhesive layer and the plant, thereby efficiently allowing the herbicide to be released and penetrate into the plant.

[0073] Secondly, pesticide-containing adhesive tapes with different specifications than those described above (Examples 7, 8 and Comparative Example 5) were prepared, and the 24-hour release rate and adhesion were measured. Practical tests were conducted using kudzu as the target plant. The evaluation results are shown in Table 3.

[0074] [Example 7] The substrate was changed from PET to Celluvian, and the pesticide concentration was set to 10% by mass. Otherwise, the pesticide-containing adhesive tape was made in the same manner as in Example 2.

[0075] [Example 8] In addition to using phosmet as a pesticide, an adhesive tape containing pesticide was made in the same manner as in Example 7.

[0076] [Comparative Example 5] Except that no pesticides were added, the pesticide-containing adhesive tape was made in the same manner as in Example 7.

[0077] Subsequently, the 24-hour release rates of ethionyl and glyphosate were determined for Examples 7 and 8 above.

[0078] (24h release rate) (1) Release rate of 24h from cypermethrin For the pesticide-containing adhesive tape in Example 7, the 24-hour release rate of ethirimol was determined. 1. Using a silicone adhesive, fix the 15 mm ϕ adhesive tape to the side of a 30 mm ϕ brown glass sample vial with the adhesive side exposed. Add 20 mL of ultrapure water (pH 6.5~7.3), keep the water temperature at about 23℃, and stir at 150 rpm with a stir bar. 2. Take 1 mL of test solution at specific time intervals, and add 1 mL of water each time. 3. Sampling time is set to 10 minutes, 30 minutes, 1 hour, 4 hours and 24 hours, and the sample solution is analyzed by HPLC. 4. Using the standard reagents of ethionamb manufactured by Fujifilm and Kosei Pure Chemical Industries Co., Ltd. as standard reagents, a calibration curve was prepared, and the amount of ethionamb in the sample solution was quantified according to the following conditions. <Analysis Conditions> Mobile phase: H₂O / acetonitrile / phosphoric acid = 80 / 20 / 0.04 vol. Column: TSgel ODS-100z 5 μm 4.6 mm × 25 cm Column temperature: 40℃ Flow rate: 1.0 mL / min Injection volume: 10 μL

[0079] (2) 24h release rate of glyphosate The pesticide-containing adhesive tape of Example 8 was tested for 24-hour release rate. 1. Using a silicone adhesive, fix the 15 mm ϕ adhesive tape to the side of a 50 mm ϕ brown glass sample bottle with the adhesive side exposed. Add 100 mL of ultrapure water (pH 6.5~7.3), keep the water temperature at about 23℃, and stir at 150 rpm with a stir bar. 2. Take 1 mL of test solution at specific time intervals, and add 1 mL of water each time. 3. Sampling time is set to 10 minutes, 30 minutes, 1 hour, 4 hours and 24 hours, and the sample solution is analyzed by HPLC. 4. Using the standard reagents of glyphosate manufactured by Fujifilm and Kosei Pure Chemical Industries Co., Ltd. as standard reagents, a calibration curve was prepared, and the amount of glyphosate in the sample solution was quantified according to the following conditions. <Analysis Conditions> Moving phase: A: Acetonitrile B: 50 mM phosphate buffer Liquid delivery: A / B=35 / 65 vol. Column: Mightysil RP-18 GP 5 μm 4.6 mm × 15 cm Column temperature: 40℃ Flow rate: 0.7 mL / min Injection volume: 5 μL

[0080] (Adhesion) The adhesive strength of the pesticide-containing adhesive tapes of Examples 7, 8 and Comparative Example 5 was measured using the same method as in Example 1.

[0081] [Practical Experiment] Practical experiments were conducted according to the following steps for Examples 7, 8, and Comparative Example 5, and the following evaluations were performed before and after the experiments. The evaluation results are shown in Table 3. A photograph of the kudzu before the experiment in Example 7 is shown in Figure 4, and a photograph of the kudzu after the experiment is shown in Figure 5. 1. The pesticide-containing adhesive tape of Examples 7, 8 and Comparative Example 5 is wrapped around the part about 2 cm away from the root of the kudzu. 2. Trial period: August 19, 2020 to September 16, 2020

[0082] (State of a withered leaf) Observe the condition of the kudzu leaves and evaluate them according to the following criteria. A: More than 80% of all leaves changed color. B: More than 50% but less than 80% of all leaves have changed color. C: Less than 50% of all leaves changed color.

[0083] (Vine State) Confirm the overall condition of the vines and evaluate them according to the following criteria. a: More than 80% of the vine has changed color and withered. b: More than 30% but less than 80% of the vine has changed color and is about to wither. c: Less than 30% of the entire vine changed color.

[0084] (Growth inhibition) Assess the growth of the vines according to the following criteria. a: The vine did not grow. b: The vines show signs of growth. c: The vines have grown somewhat.

[0085] (Sprout) Confirm whether there are new shoots on the whole kudzu plant, and evaluate it according to the following criteria. A: No new buds B: There are signs of new buds sprouting. C: New buds (leaves) sprout.

[0086] [Table 3] Example 7 Example 8 Comparative Example 5 adhesive emulsion system Acrylic emulsion adhesive II (BA series) Object Tree Ge Substrate Celluloid medicine Yi Mie Cao Jialinsai - Adhesion area 20 cm2 pesticide concentration 10 wt% - Adhesive coating amount 30 g / m2 pesticide dosage 6 mg - per 1 cm2 0.3 mg - 24h release rate 92% 95% - The state of the withered leaves (discoloration) A A C The vine's state (color change) a a c Growth inhibition (vine length) a a c sprouts A A C Adhesion N / 10 mm 6.1 4.7 5.5

[0087] As shown in Table 3, it can be seen that even when the pesticide is changed to glyphosate, the pesticide-containing adhesive tape of the present invention can still release the pesticide well. Furthermore, it can be seen that the pesticide-containing adhesive tape of the present invention also achieves good results when applied to kudzu. Moreover, by using celluloid as the substrate, not only can a good weeding effect be obtained, but also, because celluloid is biodegradable, an environmentally friendly pesticide-containing tape can be obtained.

[0088] Next, using a rubber-based emulsion adhesive as an adhesive, pesticide-containing adhesive tapes were made (Examples 9-14 and Comparative Example 6), and evaluated.

[0089] [Example 9] Except for changing the adhesive to rubber-based emulsion adhesive II, the pesticide-containing adhesive tape was made in the same manner as in Example 3.

[0090] [Example 10] Except for changing the adhesive coating amount to 150 g / m2, the pesticide-containing adhesive tape was made in the same manner as in Example 9.

[0091] [Example 11] Except that the pesticide concentration is set to 5% by mass, the pesticide-containing adhesive tape is made in the same manner as in Example 9.

[0092] [Example 12] Except for changing the adhesive coating amount to 150 g / m2, the pesticide-containing adhesive tape was made in the same manner as in Example 11.

[0093] [Example 13] Except for changing the pesticide concentration to 10% by mass, the pesticide-containing adhesive tape was made in the same manner as in Example 9.

[0094] [Example 14] Except for changing the adhesive coating amount to 150 g / m2, the pesticide-containing adhesive tape was made in the same manner as in Example 13.

[0095] [Comparative Example 6] Except that no pesticides were added, the pesticide-containing adhesive tape was made in the same manner as in Example 9.

[0096] (24h release rate and adhesion) For Examples 9-14 and Comparative Example 6 above, the 24-hour release rate and adhesion were measured using the same method as for the pesticide-containing adhesive tape in Example 1.

[0097] [Practical Experiment] Practical experiments were conducted using camellia as the target plant in accordance with Examples 9-14 and Comparative Example 6. 1. The pesticide-containing adhesive tape of Examples 9-14 and Comparative Example 6 is wrapped around the soil surface of the camellia about 2-3 cm away. 2. Trial period: January 9, 2021 to March 8, 2021 3. Since this was a winter experiment, the growth of camellias was inhibited, so the experiment was conducted in a greenhouse. The greenhouse was heated to 30°C between 7:00 AM and 6:00 PM on weekdays, and the heaters were turned off at night and on rest days.

[0098] Using the same method as the pesticide-containing adhesive tape in Example 4, the growth rate (height)%, growth rate (tree diameter)%, the condition of new shoots and residual leaves, and the leaf drop rate (%) were evaluated.

[0099] [Table 4] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 6 adhesive emulsion system Rubber-based emulsion adhesive II Object Tree Camellia Substrate PET medicine Yi Mie Cao Adhesion area 20 cm2 pesticide concentration 1 wt% 5 wt% 10 wt% - Adhesive coating amount 30 g / m2 150 g / m2 30 g / m2 150 g / m2 30 g / m2 150 g / m2 30 g / m2 pesticide dosage 0.6 mg 3 mg 3 mg 15 mg 6 mg 30 mg - per 1 cm2 0.03 mg 0.15 mg 0.15 mg 0.75 mg 0.30 mg 1.50 mg - 24h release rate 6% 7% twenty three% 20% 87% 46% - leaf fall rate 38% 50% 46% 51% 69% 69% 5% Number of tablets (before → after the experiment) 44→31 38→20 45→24 41→21 33→11 35→10 37→35 Growth rate (height) -2% 0 0 0 2% -5% -1% Growth rate (tree diameter) -13% -2% -8% -7% -3% -1% 7% sprouts A A B A B A C The state of the withered leaves (discoloration) B B B A B B C Adhesion N / 10 mm 3.8 8.4 4.2 10.1 4.3 9.0 5.5

[0100] As shown in Table 4, it can be seen that when using a rubber-based emulsion adhesive as the adhesive, the pesticide-containing adhesive tape of the present invention can also achieve good results.

[0101] Secondly, the type of pesticide was changed, and adhesive tape containing pesticide was made. The release rate and adhesion were measured over 24 hours.

[0102] [Example 15] The pesticide used was set as Datnam (insecticide), the pesticide concentration was set as 10% by mass, and the adhesive coating amount was set as 150 g / m2. Otherwise, the pesticide-containing adhesive tape was made in the same manner as in Example 2.

[0103] [Comparative Example 7] The pesticide used was set as Datnam (insecticide), and the pesticide concentration was set as 10% by mass. Otherwise, the pesticide-containing adhesive tape was made in the same manner as in Comparative Example 3.

[0104] For Example 15 and Comparative Example 7 above, the 24-hour release rate and adhesion were measured in the following manner.

[0105] (24h release rate) Dartnam 1. Using a silicone adhesive, fix the 15 mm ϕ adhesive tape to the side of a 30 mm ϕ brown glass sample vial with the adhesive side exposed. Add 20 mL of ultrapure water (pH 6.5~7.3), keep the water temperature at about 23℃, and stir at 150 rpm with a stir bar. 2. Take 1 mL of test solution at specific intervals, and add 1 mL of water each time. 3. Sampling time is set to 10 minutes, 30 minutes, 1 hour, 4 hours and 24 hours, and the sample solution is analyzed by HPLC. 4. Using the Dartnam standard reagent manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd. as the standard reagent, a calibration curve was prepared, and the amount of Dartnam in the sample solution was quantified according to the following conditions. <Analysis Conditions> Mobile phase: H₂O / acetonitrile = 90 / 10 vol. Column: TSgel ODS-100z 5 μm 4.6 mm × 25 cm Column temperature: 40℃ Flow rate: 1.0 mL / min Injection volume: 40 μL

[0106] (Adhesion) The adhesion was measured using the same method as that used for the pesticide-containing adhesive tape in Example 1.

[0107] [Table 5] Example 15 Comparative Example 7 adhesive emulsion system Hot melt system Acrylic emulsion adhesive II (BA series) acrylic adhesives Substrate PET medicine Dartnam (insecticide) pesticide concentration 10 wt% Adhesive coating amount 150 g / m2 per 1 cm2 1.5 mg 24h release rate 96% 42% Adhesion N / 10 mm 2.5 1.8

[0108] As shown in Table 5, it can be seen that a good release rate can still be obtained when the pesticide is changed to an insecticide. On the other hand, it can be seen that when using a hot-melt adhesive, even with the same pesticide concentration, the pesticide release rate is extremely low. The pesticide-containing tape of the present invention can be expected to achieve good results even when using an insecticide as the pesticide.

[0109] 10: Adhesive tape containing pesticides 11: Substrate 12: Adhesive layer

Claims

1. A pesticide-containing adhesive tape, comprising a substrate and an adhesive layer disposed on the substrate, wherein the adhesive layer contains an emulsion adhesive and a pesticide with penetrating and migrating properties, wherein the emulsion adhesive is an acrylic emulsion adhesive or a rubber emulsion adhesive with latex rubber as the main component, wherein the acrylic emulsion adhesive is polymerized by polymerizing a mixture of monomers containing the following components: (a) alkyl (meth)acrylate with 4 to 12 alkyl carbons, (b) a carboxyl-containing monomer, and (c) a copolymerizable monomer; wherein the content of (a) alkyl (meth)acrylate with 4 to 12 alkyl carbons is 50% to 99.5% by mass, the content of (b) carboxyl-containing monomer is 0.5% to 10% by mass, and the content of (c) copolymerizable monomer is 0% to 40% by mass. The aforementioned rubber-based emulsion adhesive contains latex rubber and an adhesive agent. The latex rubber is at least one of natural rubber, chloroprene rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and ethylene-vinyl acetate copolymer. The content of the latex rubber is 30% to 80% by mass relative to 100% by mass of the rubber-based emulsion adhesive, and the aforementioned pesticide is phenazine, glyphosate, or datnam.

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