Composition containing natural pyrethrin and antioxidant
The integration of natural pyrethrins with phosphorus or sulfur antioxidants in a specific composition addresses the stability issues of natural pyrethrins, enhancing both their pest control efficacy and storage stability.
Patent Information
- Application Number
- PCT/JP2024/023373
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-04
- Filing Date
- 2024-06-27
- Publication Date
- 2025-01-09
AI Technical Summary
Natural pyrethrins, used for pest control, experience a decrease in efficacy and storage stability due to their unstable chemical structures, limiting their effectiveness over time.
A composition containing natural pyrethrins combined with specific phosphorus or sulfur antioxidants, such as triisodecyl phosphite and BHT, is developed to maintain pest control efficacy and enhance storage stability.
The combination of natural pyrethrins with antioxidants like triisodecyl phosphite and BHT results in a formulation that maintains effective pest control and improves storage stability, ensuring prolonged performance.
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Figure JP2024023373_09012025_PF_FP_ABST
Abstract
Description
Composition containing natural pyrethrins and antioxidants
[0001] The present invention relates to a composition containing natural pyrethrins and an antioxidant. This application claims priority to Japanese Patent Application No. 2023-109574 filed on July 3, 2023, and Japanese Patent Application No. 2023-143206 filed on September 4, 2023, the contents of which are incorporated herein by reference.
[0002] Due to the growing consumer preference for natural products, natural pyrethrins have been attracting attention (for example, Patent Document 1). Natural pyrethrins are suitable for use in pest control, but it is known that their pest control effect or storage stability tends to decrease over time due to the instability of their chemical structure.
[0003] International Publication No. 2022 / 220294
[0004] An object of the present invention is to provide a novel composition containing natural pyrethrins that maintains its pest control effect or has excellent storage stability.
[0005] The present inventors have conducted research to provide a new composition containing natural pyrethrins, and as a result have found that a composition containing natural pyrethrins and a specific antioxidant has excellent effects, leading to the completion of the present invention.
[0006] The present invention includes, but is not limited to, the following embodiments: [1] A composition containing natural pyrethrin and one or more phosphorus-based antioxidants selected from Group P or one or more sulfur-based antioxidants selected from Group S (hereinafter referred to as the composition of the present invention): Group P: Formula (2)
[0007] (wherein R represents a C9-C14 alkyl group), the group consisting of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, tridodecyl trithiophosphite, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite; Group S: A group consisting of pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and didodecyl 3,3′-thiodipropionate. [2] The group P is 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl), tridodecyl trithiophosphite, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl The composition according to [1], wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are selected from the group consisting of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. [3] The composition according to [1] or [2], wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are selected from the group consisting of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. L The composition according to [1], wherein the phosphorus-based antioxidant is one or more selected from the group P L: the group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite). [5] The composition according to [4], which contains a phenolic antioxidant. [6] A pest control formulation for thermal evaporation, which contains the composition according to [4] or [5] and a paraffinic solvent. [7] A method for controlling mosquitoes, which uses the composition according to either [4] or [5] or the pest control formulation for thermal evaporation according to [6]. [8] The composition according to [1], wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite. [9] The composition according to [8], which contains a phenolic antioxidant. The present invention further includes, but is not limited to, the following aspects. <1> A composition containing natural pyrethrin and one or more phosphorus-based antioxidants selected from Group P or one or more sulfur-based antioxidants selected from Group S: Group P: Formula (1)
[0008] [In the formula, R 1 and R 2and are the same or different and represent a C9-C14 alkyl group, the group consisting of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, tridodecyl trithiophosphite, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite; Group S: A group consisting of pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and didodecyl 3,3′-thiodipropionate. <2> Group P is 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl), tridodecyl trithiophosphite, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl <4> The composition according to <1>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are selected from the group consisting of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. <5> The composition according to <1> or <2>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are selected from the group consisting of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. L The composition according to <1>, wherein the phosphorus-based antioxidant is one or more selected from the group P L: the group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite). <5> The composition according to <4>, containing a phenolic antioxidant. <6> A pest control formulation for thermal evaporation, containing the composition according to <4> or <5> and a paraffinic solvent. <7> A method for exterminating mosquitoes, using the composition according to <4> or <5> or the pest control formulation for thermal evaporation according to <6>. <8> The one or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group S are selected from group P. M The composition according to <1>, wherein the phosphorus-based antioxidant is one or more selected from the group P M The group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite. <9> The composition according to <8>, which contains a phenolic antioxidant. <10> The composition according to <1>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are compounds represented by formula (1). <11> The composition according to <1>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane or 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. <12> The composition according to <1>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. U The composition according to <1>, wherein the antioxidant is one or more phosphorus-based antioxidants selected from Group P or one or more sulfur-based antioxidants selected from Group S: U<13> The group consisting of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphinate, and tridodecyl trithiophosphite. U The composition according to <12>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are one or more sulfur-based antioxidants selected from Group S. <14> The composition according to <12>, wherein the one or more phosphorus-based antioxidants selected from Group P or the one or more sulfur-based antioxidants selected from Group S are one or more sulfur-based antioxidants selected from Group S. <15> The composition according to <14>, wherein the one or more sulfur-based antioxidants selected from Group S are pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, or 2,4-bis[(dodecylthio)methyl]-6-methylphenol. <16> The composition according to any one of <12> to <15>, which contains a phenol-based antioxidant. <17> The composition according to any one of <12> to <15>, which contains citric acid. <18> The composition according to <16>, which contains citric acid.
[0009] According to the present invention, a novel composition containing natural pyrethrins can be provided, which maintains its pest control effect and has excellent storage stability.
[0010] Fig. 1 is a cross-sectional view of a heat-transpiration type insecticide device using a chemical solution bottle, Fig. 2 is a perspective view of a heat-transpiration type insecticide device using a pest control mat, and Fig. 3 is a perspective view of an insect repellent equipped with a resin formulation.
[0011] The natural pyrethrins used in the present invention contain six active compounds: pyrethrin I, pyrethrin II, cinerin I, cinerin II, jasmoline I, and jasmoline II. Natural pyrethrins are typically available as pyrethrum dry powder or as an extract obtained by extracting only the flower buds of pyrethrum (scientific name: Tanacetum cinerariifolium or Chrysanthemum cinerariaefolium) from which only the flower buds have been harvested, dried, and ground. The powder is then extracted with an appropriate solvent (also called solvent), such as an organic solvent such as methanol, that dissolves the active ingredients. In addition to the six compounds, natural pyrethrins may also contain plant-derived impurities (such as fatty acids and flavonoids).In addition to the white daisy, other plants known to produce natural pyrethrins include Calendula officinalis, Chrysanthemum coccinum, Tagetes erecta, Tagetes minuta, Zinnia elegans, and Zinnia linnearis (Reference 1: Adnane, H. Alain, C. & Chantal, B. 2000. The Production of Pyrethrins by Plant Cell and Tissue Cultures of Chrysanthemum cinerariaefolium and Tagetes Species. Critical Reviews in Plant Sciences, 19(1):69-89; Reference 2: Kudakasseril, GJ and Staba, EJ 1988. Insecticidal phytochemicals. In: Cell Culture and Somatic Cell Genetics of Plants. pp. 537-552. Constabel, F. and Vasil, IK, Eds., Academic Press, New York, Reference 3: John E. Casida, Gary B. Quistad. 1995. PYRETHRUM FLOWERS, Production, Chemistry, Toxicology, and Uses. pp. 123-125, Oxford University Press.).
[0012] The plant species and varieties that serve as the source of the natural pyrethrins used in the present invention are not limited to those described above. The cultivation method, cultivation conditions (weather, place of origin, soil type, etc.), harvest time, harvest part, harvesting method, washing method, extraction method, and purification method of the plant are not particularly limited. The natural pyrethrins used in the present invention also include, for example, natural pyrethrins obtained using a vector into which a gene encoding a pyrethrin biosynthetic enzyme has been inserted.
[0013] The mass ratios of the six types of compounds, pyrethrin I, pyrethrin II, cinerin I, cinerin II, jasmolin I, and jasmolin II, in natural pyrethrins are not particularly limited, and can be set at any mass ratio within the range of 0.001 to 99% by mass relative to the total amount of natural pyrethrins. Typically, however, the natural pyrethrins are contained in mass ratios of 10 to 70% by mass of pyrethrin I, 10 to 70% by mass of pyrethrin II, 1 to 20% by mass of cinerin I, 1 to 20% by mass of cinerin II, 1 to 20% by mass of jasmolin I, and 1 to 20% by mass of jasmolin II relative to the total amount of natural pyrethrins. Specifically, the following blending ratios (mass ratios) are exemplified, for example, [pyrethrin I:cinerin I:jasmolin I:pyrethrin II:cinerin II:jasmolin II] = 38.0:7.3:4.0:35.0:11.7:4.0 (Reference 3).
[0014] Examples of natural pyrethrins include those containing pyrethrin I (the total amount of pyrethrin I, cinerin I, and jasmolin I) and pyrethrin II (the total amount of pyrethrin II, cinerin II, and jasmolin II) in an amount of 20 to 40% by mass of pyrethrin I and 12 to 31% by mass of pyrethrin II, relative to the total amount of natural pyrethrins. The total amount of pyrethrin I and pyrethrin II in the natural pyrethrin is typically 10 to 99% by mass, preferably 15 to 90% by mass, and more preferably 20 to 85% by mass, relative to the total amount of natural pyrethrins. Examples of such natural pyrethrins include those in which the content (% by mass) of pyrethrin I is 20 to 40% and the content (% by mass) of pyrethrin II is 12 to 31%.
[0015] Phosphorus-based antioxidants will now be described. Examples of compounds represented by formula (1) include 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is commercially available, for example, as JPE-10 (manufactured by Johoku Chemical Industry Co., Ltd.). 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is commercially available, for example, as JPE-13R (manufactured by Johoku Chemical Industry Co., Ltd.). 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is commercially available, for example, as a product manufactured by Tokyo Chemical Industry Co., Ltd. or as Adekastab PEP24 (manufactured by ADEKA). Tris(nonylphenyl)phosphite is commercially available, for example, as JP-351 (manufactured by Johoku Chemical Industry Co., Ltd.). Triphenyl phosphite is commercially available, for example, as triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.) or as Adekastab TPP (manufactured by ADEKA). Tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate is commercially available, for example, as HOSTANOX™ P-EPQ™ (manufactured by Clariant Chemicals). Tridodecyl trithiophosphite is commercially available, for example, as JPS-312 (manufactured by Johoku Chemical Industry Co., Ltd.). Triisodecyl phosphite is commercially available, for example, as Adeka STAB 3010 (manufactured by ADEKA). Diphenylisodecyl phosphite is commercially available, for example, as Adeka STAB 135A (manufactured by ADEKA). 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is commercially available, for example, as JPH-1200 (manufactured by Johoku Chemical Industry Co., Ltd.). Tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite is commercially available, for example, as Adeka STAB 1500 (manufactured by ADEKA).
[0016] Sulfur-based antioxidants will now be described. Pentaerythritol tetrakis[3-(dodecylthio)propionate] is commercially available, for example, as Sumilizer™ TP-D (manufactured by Sumitomo Chemical) and Adekastab AO-412S (manufactured by ADEKA). 2-Mercaptobenzimidazole is commercially available, for example, as manufactured by Tokyo Chemical Industry Co., Ltd. 2,4-bis[(dodecylthio)methyl]-6-methylphenol is commercially available, for example, as Irganox™ 1726 (manufactured by BASF Japan). 3,3'-Didodecyl thiodipropionate is commercially available, for example, as manufactured by Tokyo Chemical Industry Co., Ltd.
[0017] The composition of the present invention may contain a phenolic antioxidant. Examples of such phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol (hereinafter sometimes abbreviated as BHT), butylhydroxyanisole (hereinafter sometimes abbreviated as BHA), and 2,2'-methylenebis(6-tert-butyl-4-methylphenol). 2,2'-methylenebis(6-tert-butyl-4-methylphenol) or BHT is preferred, and BHT is particularly preferred. BHT and BHA are commercially available, for example, from Kanto Chemical. 2,2'-methylenebis(6-tert-butyl-4-methylphenol) is commercially available as Sumilizer (trademark) MDP-S.
[0018] The composition of the present invention can be applied to pest control formulations for thermal evaporation, pest control mat formulations, resin formulations, manufacturing use products (also referred to as MUPs), and the like, which will be described later.
[0019] <Pest Control Formulation for Thermal Transpirability> One embodiment of the present invention is a pest control formulation for thermal transpirability containing natural pyrethrins and an antioxidant. The pest control formulation for thermal transpirability according to one embodiment of the present invention is a formulation that can be used in a thermal transpirability insecticide device 100, such as that shown in FIG. 1 . A solution 1 containing a thermal transpirability composition is filled in a chemical bottle 4. In this specification, compositions suitable for use in pest control formulations for thermal transpirability applied to a thermal transpirability insecticide device using a chemical bottle may be referred to as a thermal transpirability composition. A portion of an absorbent wick 3 is immersed in the solution 1, and the absorbent wick is allowed to absorb a solution containing the thermal transpirability composition, and the upper portion of the absorbent wick can be heated by a heating element 2. By indirectly heating the upper portion of the absorbent wick to a temperature of approximately 60°C to approximately 150°C using the heating element 2, the thermal transpirability composition absorbed into the absorbent wick is evaporated into the atmosphere, thereby enabling pest control. The pest control formulation for thermal evaporation according to one embodiment of the present invention can be applied to any conventionally known thermal evaporation type insecticidal device, and can exhibit excellent effects, without being limited to the device shown in Figure 1. Thermal evaporation type insecticidal devices to which the pest control formulation for thermal evaporation according to the present invention can be applied are also described in, for example, JP-B No. 52-12106, JP-A No. 58-45670, and JP-A No. 2012-176947.
[0020] In the pest control formulation for thermal evaporation of the present invention, a composition containing natural pyrethrins and an antioxidant (also referred to as the thermal evaporation composition) is prepared in the form of a solution (Solution 1) containing the composition and used. An oily or aqueous solvent is used as the solvent (also referred to as the solvent) for preparing the pest control formulation for thermal evaporation. A pest control formulation for thermal evaporation can be prepared by dissolving the thermal evaporation composition in such a solvent. When an oily solvent is used, an oily solvent having a boiling point of 350°C or less is typically used. While various organic solvents, typically hydrocarbon solvents, can be used as such oily solvents, aliphatic hydrocarbon solvents (paraffinic solvents or unsaturated aliphatic hydrocarbon solvents, or mixtures thereof) with a boiling point range of 150 to 350°C are particularly preferred. Examples of such solvents include paraffinic solvents such as n-paraffin and isoparaffin; deodorized kerosene; and sewing machine oil (e.g., Sewing Lube (manufactured by ENEOS Corporation)), among which paraffinic solvents are preferred. Specific examples of paraffin-based solvents include No. 0 Solvent H (manufactured by ENEOS Corporation), No. 0 Solvent M (manufactured by ENEOS Corporation), No. 0 Solvent L (manufactured by ENEOS Corporation), IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.), Norpar 12 (manufactured by Exxon Mobil Corporation), Norpar 13 (manufactured by Exxon Mobil Chemical Co., Ltd.), Norpar 15 (manufactured by Exxon Mobil Corporation), Isopar M (manufactured by Exxon Mobil Corporation), Isopar L (manufactured by Exxon Mobil Corporation), Isopar V (manufactured by Exxon Mobil Corporation), and Isopar G (manufactured by Exxon Mobil Corporation). Examples of organic solvents other than the hydrocarbon-based solvents include glycerin, propylene glycol, methanol, acetone, xylene, chlorthene, isopropanol, and chloroform. When an aqueous solvent is used, glycol ether and water are typically used. Examples of such glycol ethers include ethylene glycol ethers, propylene glycol ethers, and dialkyl glycol ethers, with ethylene glycol ethers being preferred.Among ethylene glycol-based ethers, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether are preferred. The glycol ethers can be used alone or in combination. The mass ratio of glycol ether to water is typically in the range of 1:0.4 to 1:8.5, preferably 1:1 to 1:8.5, and more preferably 1:1.4 to 1:3.6. The solvent may further contain a cosolvent (also referred to as auxiliary solvent). Examples of the cosolvent include diisopropyl adipate, diisodecyl adipate, diisobutyl adipate, isopropyl myristate, isopropanol, benzyl acetate, cellulose nanofiber, ethanol, sucrose fatty acid esters, sorbitan fatty acid esters, propylene carbonate, 1,3-butylene glycol, and polyoxyethylene hydrogenated castor oil. The cosolvent may be different from the solvent used. For example, when a paraffin-based solvent is used as the solvent, diisopropyl adipate or isopropyl myristate is preferred as the co-solvent. The solvent content in the pest control formulation for thermal evaporation is typically 65 to 99.96% by mass, preferably 80 to 98.5% by mass, based on the total amount of the pest control formulation for thermal evaporation. When the pest control formulation for thermal evaporation further contains a co-solvent, the co-solvent content can typically be 5 to 30% by mass, preferably 10 to 25% by mass, based on the total amount of the pest control formulation for thermal evaporation. The concentration of the composition containing natural pyrethrin and an antioxidant in the pest control formulation for thermal evaporation (also referred to as the thermal evaporation composition) is typically prepared to be about 1 to 50% by mass, preferably about 1 to 40% by mass, and more preferably about 4 to 15% by mass, based on the total amount of the pest control formulation for thermal evaporation. Here, the sum of the content (content rate) of the solvent and the concentration of the composition for thermal evaporation does not exceed 100% by mass. When a co-solvent is further contained, the sum of the content (content rate) of the solvent, the content of the co-solvent, and the concentration of the composition for thermal evaporation does not exceed 100% by mass.The pest control formulation for thermal vaporization of the present invention may also contain other ingredients such as a thickener, a surfactant, a stabilizer, a preservative, or a synergist.
[0021] In the pest control formulation for thermal evaporation of the present invention, one embodiment of the composition containing a natural pyrethrin and a phosphorus-based antioxidant (also referred to as a composition for thermal evaporation) is a composition containing a natural pyrethrin and one or more phosphorus-based antioxidants selected from the group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite). Another embodiment of the composition containing natural pyrethrins and a phosphorus-based antioxidant (also referred to as a composition for heated evaporation) is a composition containing natural pyrethrins and 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2, and one or more phosphorus-based antioxidants selected from the group consisting of 4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, tridodecyl trithiophosphite, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. Another embodiment of the composition containing natural pyrethrins and a phosphorus-based antioxidant (also referred to as a composition for thermal evaporation) is a composition further containing a phenolic antioxidant such as BHT.
[0022] One embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 4 parts by mass of a phosphorus-based antioxidant, and 0 to 10 parts by mass, 0.01 to 10 parts by mass, preferably 0 to 8 parts by mass, 0.5 to 8 parts by mass, and more preferably 0 to 7 parts by mass, or 1 to 7 parts by mass of a phenol-based antioxidant such as BHT, relative to 0.6 parts by mass of natural pyrethrin.
[0023] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 4 parts by mass of triisodecyl phosphite, and 0 to 10 parts by mass, 0.01 to 10 parts by mass, preferably 0 to 8 parts by mass, 0.5 to 8 parts by mass, and more preferably 0 to 7 parts by mass, or 1 to 7 parts by mass of BHT, relative to 0.6 parts by mass of natural pyrethrin.
[0024] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 part by mass of natural pyrethrin, 0.01 to 4 parts by mass of triisodecyl phosphite, and 0 to 7 parts by mass of BHT.
[0025] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 part by mass of natural pyrethrin, 0.01 to 4 parts by mass of triisodecyl phosphite, and 1 to 7 parts by mass of BHT.
[0026] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 part by mass of natural pyrethrin, 0.01 to 10 parts by mass of diphenylisodecyl phosphite, and 0 to 10 parts by mass of BHT.
[0027] Yet another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass, preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecylphosphite), and 0 to 10 parts by mass, 0.01 to 10 parts by mass, preferably 0 to 8 parts by mass, 0.5 to 8 parts by mass, and more preferably 0 to 7 parts by mass or 1 to 7 parts by mass of BHT, relative to 0.6 parts by mass of natural pyrethrin.
[0028] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.1 to 2 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and 0 to 7 parts by mass of BHT.
[0029] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.1 to 2 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and 1 to 7 parts by mass of BHT.
[0030] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 0 to 10 parts by mass of BHT relative to 0.6 parts by mass of natural pyrethrin.
[0031] Another embodiment of the composition for heating evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 0 to 10 parts by mass of BHT relative to 0.6 parts by mass of natural pyrethrin.
[0032] Another embodiment of the composition for heating evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 0 to 10 parts by mass of BHT relative to 0.6 parts by mass of natural pyrethrin.
[0033] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.01 to 10 parts by mass of tris(nonylphenyl)phosphite, and 0 to 10 parts by mass of BHT.
[0034] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of triphenyl phosphite and 0 to 10 parts by mass of BHT relative to 0.6 part by mass of natural pyrethrin.
[0035] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.01 to 10 parts by mass of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate, and 0 to 10 parts by mass of BHT.
[0036] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of tridodecyl trithiophosphite and 0 to 10 parts by mass of BHT relative to 0.6 part by mass of natural pyrethrin.
[0037] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.01 to 10 parts by mass of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and 0 to 10 parts by mass of BHT.
[0038] In the pest control formulation for thermal evaporation of the present invention, the composition containing a natural pyrethrin and a phosphorus-based antioxidant (also referred to as a composition for thermal evaporation) may be embodied as follows: [Aspect L1] A composition containing a natural pyrethrin and triisodecyl phosphite.
[0039] In the pest control formulation for thermal evaporation of the present invention, the composition containing natural pyrethrin, a phenolic antioxidant, and a phosphorus-based antioxidant (also referred to as a thermal evaporation composition) can be exemplified by the following compositions: [Aspect LB1] A composition containing natural pyrethrin, a phenolic antioxidant, and triisodecyl phosphite. [Aspect LB2] A composition containing natural pyrethrin, BHT, and triisodecyl phosphite. [Aspect LB3] A composition containing 0.6 parts by mass of natural pyrethrin, 5 parts by mass of BHT, and 2 parts by mass of triisodecyl phosphite. [Aspect LB4] A composition containing 0.6 parts by mass of natural pyrethrin, 0.5 parts by mass of BHT, and 0.5 parts by mass of triisodecyl phosphite.
[0040] In one embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrins is 0.01 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, relative to the total amount of the pest control formulation for thermal evaporation of the present invention; the content of phosphorus-based antioxidants is 0.01 to 10% by mass, preferably 0.01 to 5% by mass, and more preferably 0.01 to 4% by mass; the content of phenolic antioxidants such as BHT is 0 to 10% by mass, 0.01 to 10% by mass, preferably 0 to 8% by mass, 0.5 to 8% by mass, more preferably 0 to 7% by mass, or 1 to 7% by mass; and the content of solvents such as paraffinic solvents is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 85 to 99.9% by mass. Here, the sum of the content of natural pyrethrins, the content of phosphorus-based antioxidants, the content of phenolic antioxidants such as BHT, and the content of solvents such as paraffin-based solvents does not exceed 100% by mass.
[0041] In another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrins, relative to the total amount of the pest control formulation for thermal evaporation, is 0.01 to 45% by mass, preferably 0.05 to 10% by mass, more preferably 0.1 to 1% by mass; the content of triisodecyl phosphite, is 0.01 to 10% by mass, preferably 0.01 to 5% by mass, more preferably 0.01 to 4% by mass; the content of BHT, is 0 to 10% by mass, 0.01 to 10% by mass, preferably 0 to 8% by mass, 0.5 to 8% by mass, more preferably 0 to 7% by mass, 1 to 7% by mass; and the content of paraffinic solvents (e.g., Isopar G, Isopar M, Isopar L, or mixtures thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, more preferably 88 to 99.9% by mass.
[0042] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of triisodecyl phosphite is 0.01 to 4 mass %, the content of BHT is 0 to 7 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 88 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0043] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of triisodecyl phosphite is 0.01 to 4 mass %, the content of BHT is 1 to 7 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 88 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0044] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of diphenylisodecyl phosphite is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0045] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of diphenylisodecyl phosphite is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0046] In another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrins, relative to the total amount of the pest control formulation for thermal evaporation, is 0.01 to 45% by mass, preferably 0.05 to 10% by mass, more preferably 0.1 to 1% by mass; the content of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 0.01 to 10% by mass, preferably 0.01 to 3% by mass, more preferably 0.1 to 2% by mass; the content of BHT is 0 to 10% by mass, 0.01 to 10% by mass, preferably 0 to 8% by mass, 0.5 to 8% by mass, more preferably 0 to 7% by mass, 1 to 7% by mass; and the content of paraffinic solvents (e.g., Isopar G, Isopar M, Isopar L, or mixtures thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, more preferably 90 to 99.8% by mass.
[0047] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 0.1 to 2 mass %, the content of BHT is 0 to 7 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 90 to 99.8 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0048] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 0.1 to 2 mass %, the content of BHT is 1 to 7 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 90 to 99.8 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0049] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0050] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0051] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0052] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0053] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0054] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0055] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of tris(nonylphenyl)phosphite is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0056] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of tris(nonylphenyl)phosphite is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0057] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of triphenyl phosphite is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0058] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of triphenyl phosphite is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0059] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0060] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0061] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of tridodecyl trithiophosphite is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0062] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of tridodecyl trithiophosphite is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0063] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0064] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0065] In the pest control formulation for thermal evaporation of the present invention, examples of the pest control formulation for thermal evaporation containing natural pyrethrin and a phosphorus-based antioxidant include the following compositions: [Aspect LF1] A pest control formulation for thermal evaporation containing natural pyrethrin, triisodecyl phosphite, and a paraffin-based solvent.
[0066] Among the pest control formulations for thermal evaporation of the present invention, examples of the pest control formulation for thermal evaporation containing natural pyrethrin, a phenolic antioxidant, and a phosphorus-based antioxidant include the following compositions: [Aspect LBF1] A pest control formulation for thermal evaporation containing natural pyrethrin, a phenolic antioxidant, triisodecyl phosphite, and a paraffinic solvent; [Aspect LBF2] A pest control formulation for thermal evaporation containing natural pyrethrin, BHT, triisodecyl phosphite, and a paraffinic solvent; [Aspect LBF3] A pest control formulation for thermal evaporation containing 1.26% by mass of natural pyrethrin (content 47.5%, 0.6% by mass as the natural pyrethrin active ingredient), 5% by mass of BHT, 2% by mass of triisodecyl phosphite, and 91.74% by mass of paraffinic solvent, relative to the total amount of the pest control formulation for thermal evaporation. [Aspect LBF4] A pest control formulation for thermal evaporation containing 1.26 parts by mass of natural pyrethrin (47.5% content, 0.6 parts by mass as natural pyrethrin active ingredient), 5 parts by mass of BHT, 2 parts by mass of triisodecyl phosphite, and 91.74 parts by mass of paraffinic solvent. [Aspect LBF5] A pest control formulation for thermal evaporation containing 0.6% by mass of natural pyrethrin, 5% by mass of BHT, 2% by mass of triisodecyl phosphite, and 92% by mass of paraffinic solvent, relative to the total amount of the pest control formulation for thermal evaporation. [Aspect LBF6] A pest control formulation for thermal evaporation containing 0.6 parts by mass of natural pyrethrin, 5 parts by mass of BHT, 2 parts by mass of triisodecyl phosphite, and 92 parts by mass of paraffinic solvent. [Aspect LBF7] A pest control formulation for thermal evaporation containing, relative to the total amount of the pest control formulation, 1.26% by mass of natural pyrethrin (content 47.5%, 0.6% by mass as the natural pyrethrin active ingredient), 5% by mass of BHT, 2% by mass of triisodecyl phosphite, and 91.74% by mass of Isopar G. [Aspect LBF8] A pest control formulation for thermal evaporation containing 1.26 parts by mass of natural pyrethrin (content 47.5%, 0.6 parts by mass as the natural pyrethrin active ingredient), 5 parts by mass of BHT, 2 parts by mass of triisodecyl phosphite, and 91.74 parts by mass of Isopar G. [Aspect LBF9] A pest control formulation for thermal evaporation containing 0.6% by mass of natural pyrethrin, 5% by mass of BHT, 2% by mass of triisodecyl phosphite, and 92% by mass of Isopar G relative to the total amount of the pest control formulation for thermal evaporation.[Embodiment LBF10] A pest control formulation for thermal evaporation containing 0.6 parts by weight of natural pyrethrin, 5 parts by weight of BHT, 2 parts by weight of triisodecyl phosphite, and 92 parts by weight of Isopar G.
[0067] In the pest control formulation for thermal evaporation of the present invention, one embodiment of the composition containing natural pyrethrin and a sulfur-based antioxidant (also referred to as a composition for thermal evaporation) is a composition containing natural pyrethrin and one or more phosphorus-based antioxidants selected from the group consisting of didodecyl 3,3'-thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, and 2,4-bis[(dodecylthio)methyl]-6-methylphenol. Another embodiment of the composition containing natural pyrethrin and a sulfur-based antioxidant (also referred to as a composition for thermal evaporation) is a composition further containing a phenolic antioxidant such as BHT.
[0068] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 part by mass of natural pyrethrin, 0.01 to 10 parts by mass of didodecyl 3,3'-thiodipropionate, and 0 to 10 parts by mass of BHT.
[0069] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 parts by mass of natural pyrethrin, 0.01 to 10 parts by mass of pentaerythritol tetrakis[3-(dodecylthio)propionate], and 0 to 10 parts by mass of BHT.
[0070] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.6 part by mass of natural pyrethrin, 0.01 to 10 parts by mass of 2-mercaptobenzimidazole, and 0 to 10 parts by mass of BHT.
[0071] Another embodiment of the composition for thermal evaporation of the present invention is a composition containing 0.01 to 10 parts by mass of 2,4-bis[(dodecylthio)methyl]-6-methylphenol and 0 to 10 parts by mass of BHT relative to 0.6 parts by mass of natural pyrethrin.
[0072] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of didodecyl 3,3'-thiodipropionate is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0073] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of didodecyl 3,3'-thiodipropionate is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0074] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of pentaerythritol tetrakis[3-(dodecylthio)propionate] is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0075] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of pentaerythritol tetrakis[3-(dodecylthio)propionate] is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0076] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of 2-mercaptobenzimidazole is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0077] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 2-mercaptobenzimidazole is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0078] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 45% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 1% by mass, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.01 to 10% by mass, the content of BHT is 0 to 10% by mass, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 55 to 99.98% by mass, preferably 79 to 99.9% by mass, and more preferably 79 to 99.9% by mass, relative to the total amount of the pest control formulation for thermal evaporation.
[0079] In yet another embodiment of the pest control formulation for thermal evaporation of the present invention, the content of natural pyrethrin is 0.1 to 1 mass %, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.01 to 10 mass %, the content of BHT is 0 to 10 mass %, and the content of paraffinic solvent (e.g., Isopar G, Isopar M, Isopar L, or a mixture thereof) is 79 to 99.9 mass %, relative to the total amount of the pest control formulation for thermal evaporation.
[0080] Furthermore, the heating element (heating element 2) used in the heat evaporation type insecticide device is usually a heating element that generates heat when electricity is passed through it, but is not limited to this, and any known heating element can be used, such as an air oxidation heating element, a heating element that uses a platinum catalyst, etc.
[0081] The liquid-absorbent wick 3 is generally made of a porous material. Examples of such porous materials include inorganic powders such as clay, talc, kaolin, silica, calcite, diatomaceous earth, gypsum, perlite, bentonite, acid clay, glass fiber, or asbestos, which are bound and molded with a glue such as carboxymethyl cellulose, starch, gum arabic, gelatin, or polyvinyl alcohol; inorganic substances such as clay, talc, bentonite, alumina, silica, or calcite, which are solidified into a core shape and baked; resins molded into a core shape; and bundles of glass fiber. The liquid-absorbent wick may also contain dyes, preservatives, antioxidants, or the like, as appropriate. These can be incorporated by mixing the inorganic powder with the glue during the binding process.
[0082] Target pests for control by the pest control formulation for thermal vaporization of the present invention include various harmful insects and arthropods such as mites, particularly harmful flying pests, such as Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, and Culex molestus, Aedes mosquitoes such as Aedes aegypti and Aedes albopictus, Anopheles mosquitoes such as Anopheles sinensis, midges, house flies such as Musca domestica, Musca domestica, and Musca canina, blow flies, flesh flies, fruit flies, moth flies, phorid flies, horseflies, black flies, stable flies, and midges. Among these, mosquitoes such as Culex pipiens, Aedes mosquitoes, and Anopheles mosquitoes are particularly suitable as target pests for control.
[0083] One embodiment of the present invention is a method for controlling target pests, comprising heating a pest control formulation for thermal evaporation to evaporate an effective amount of the composition for thermal evaporation into the atmosphere. Another embodiment of the present invention is a method for controlling target pests, in which heating the pest control formulation for thermal evaporation comprises allowing an absorbent wick to absorb a solution containing the composition for thermal evaporation, and heating an upper part of the absorbent wick with a heating element. Another embodiment of the present invention is a method for controlling target pests, in which heating an upper part of the absorbent wick with a heating element comprises indirectly heating the upper part of the absorbent wick with a heating element to a temperature of about 60°C to about 150°C. In yet another embodiment of the present invention, the method for controlling target pests is a method for exterminating mosquitoes. In this specification, "control" is a concept that includes extermination, repellency, and prevention. "Extermination" refers to a concept including killing, knocking down, driving away, or keeping away the target pests, and it is preferable to kill or knock down the target pests.
[0084] <Pest Control Mat Formulation> One embodiment of the present invention is a pest control mat formulation containing natural pyrethrin and an antioxidant. The pest control mat is also sometimes referred to as an electric mosquito repellent mat. The pest control mat formulation of one embodiment of the present invention is a formulation that can be applied to a pest control mat 11 used in a thermal evaporation type insecticide device 200, for example, as shown in FIG. 2. In the thermal evaporation type insecticide device 100 of FIG. 2, a pest control mat 11 holding the pest control mat formulation is placed on a hot plate 10, and the hot plate is heated to approximately 140 to 200°C, thereby evaporating the pest control mat composition held in the pest control mat into the atmosphere, thereby controlling pests. Furthermore, the pest control mat formulation of one embodiment of the present invention is a formulation that can be applied to a pest control mat used in a thermal evaporation type insecticide device, for example, as described in JP-A-11-510055. The thermal evaporation type insecticide device described in JP-A-11-510055 burns a fuel such as butane gas and heats the pest control mat to approximately 120-200°C, thereby evaporating the pest control mat composition held in the pest control mat into the atmosphere, thereby controlling pests. That is, while the thermal evaporation type insecticide device 200 shown in FIG. 2 heats the hot plate 10 by electrical heating, the thermal evaporation type insecticide device described in JP-A-11-510055 heats the hot plate within the device by burning a fuel such as butane gas. While the two devices differ in heat source and heating temperature, they share the same principle of evaporating the pest control mat composition held in the pest control mat into the atmosphere by heating. In this specification, a composition suitable for use in a pest control mat used in a thermal evaporation type insecticide device that uses a pest control mat may be referred to as a pest control mat composition. The formulation for pest control mats of one embodiment of the present invention can be applied to conventionally known pest control mats, and is not limited to the device shown in Figure 2, but can also be applied to conventionally known thermal evaporation type insecticidal devices that use pest control mats, and can produce excellent effects in all cases.
[0085] Another embodiment of the present invention is a pest control mat having a formulation for pest control mats held thereon.
[0086] The pest control mat comprises a fibrous or porous carrier holding a pest control mat formulation containing natural pyrethrin and an antioxidant. In one embodiment of the present invention, the pest control mat formulation typically contains 5 to 40 mass% of the pest control mat composition relative to the total amount of the pest control mat formulation, and may further contain a solvent (also referred to as a solvent), a pigment, a stabilizer, a fragrance, etc. as appropriate.
[0087] Examples of such solvents include ester-based solvents and hydrocarbon-based solvents. Specific examples of ester-based solvents include diisodecyl phthalate, di-2-ethylhexyl phthalate, diisopropyl adipate, diisodecyl adipate, di-n-octyl sebacate, diisononyl adipate, di-2-ethylhexyl sebacate, di-2-ethylhexyl azelate, di-n-hexyl azelate, di-2-ethylhexyl dodecanoate, dibutoxyethoxyethyl adipate, isopropyl palmitate, dioctyl adipate, di-n-butyl sebacate, acetyl tributyl citrate, di-2-ethylhexyl maleate, and isopropyl myristate. Examples of hydrocarbon-based solvents include n-paraffin-based solvents, isoparaffin-based solvents, and naphthenic solvents. Specific examples of n-paraffin solvents include dodecane, tridecane, tetradecane, pentadecane, Norpar 13 (trade name, manufactured by ExxonMobil Chemical Co., Ltd.), Norpar 15 (trade name, manufactured by ExxonMobil Chemical Co., Ltd.), n-paraffin grade M (trade name, manufactured by Nippon Oil Corporation), n-paraffin grade H (trade name, manufactured by Nippon Oil Corporation), and Neothiosol (trade name, manufactured by Chuo Kasei Co., Ltd.). Examples of isoparaffin solvents include Isopar M (trade name, manufactured by Ethanol Co., Ltd.). Examples of naphthenic solvents include ExxonMobil (trade name), ExxonMobil (manufactured by ExxonMobil), Isopar V (trade name, ExxonMobil), IP Solvent 2028 (trade name, ExxonMobil), IP Solvent 2835 (trade name, ExxonMobil), and Shellsol™ (trade name, Exxon Chemicals Japan Co., Ltd.), and examples of naphthenic solvents include ExxonMobil (trade name), ExxonMobil (trade name), and ExxonMobil (trade name). Kerosene can also be used.The solvent may further contain a co-solvent (also referred to as auxiliary solvent). Examples of the co-solvent include diisopropyl adipate, diisodecyl adipate, diisobutyl adipate, isopropyl myristate, isopropanol, benzyl acetate, cellulose nanofiber, ethanol, sucrose fatty acid ester, sorbitan fatty acid ester, propylene carbonate, 1,3-butylene glycol, and polyoxyethylene hydrogenated castor oil. A solvent different from the solvent used may be selected as the co-solvent. For example, when an n-paraffinic solvent, an isoparaffinic solvent, or a naphthenic solvent is used as the solvent, diisopropyl adipate, isopropyl myristate, or the like is preferred as the co-solvent.
[0088] The pest control mat formulation typically contains one or more of these solvents. The content is typically about 50 to 95% by mass, based on the total amount of the pest control mat formulation. When the pest control mat formulation further contains a cosolvent, the content of the cosolvent is typically 5 to 30% by mass, preferably 10 to 25% by mass, based on the total amount of the pest control mat formulation. The concentration of the composition containing natural pyrethrin and antioxidant (also referred to as the pest control mat composition) in the pest control mat formulation is typically prepared to be about 1 to 50% by mass, preferably about 1 to 40% by mass, and more preferably about 4 to 40% by mass, based on the total amount of the pest control mat formulation. Here, the sum of the solvent content (content rate) and the concentration of the pest control mat composition does not exceed 100% by mass. When a co-solvent is further contained, the sum of the content (content rate) of the solvent, the content of the co-solvent and the concentration of the composition for a pest control mat does not exceed 100% by mass.
[0089] Examples of antioxidants include phosphorus-based antioxidants such as triisodecyl phosphite, diphenylisodecyl phosphite, 4,4′-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4′-isopropylidene diphenyl diphosphite, and phenol-based antioxidants such as BHA, BHT, and 2,2′-methylenebis(6-tert-butyl-4-methylphenol).
[0090] Examples of dyes include anthraquinone-based blue dyes such as 1,4-dibutylaminoanthraquinone, 1,4-diisopropylaminoanthraquinone, 1,4-bis(2,6-diethyl-4-methylphenylamino)anthraquinone, 1-methylamino-4-orthotolylaminoanthraquinone, 1-methylamino-4-metatolylaminoanthraquinone, and 1-methylamino-4-paratolylaminoanthraquinone. These dyes may be used alone or in combination of two or more, or may be used in combination with other dyes of different colors. Examples of stabilizers include ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers.
[0091] In one embodiment of the composition containing natural pyrethrin and an antioxidant (also referred to as a composition for pest control mats) in the formulation for pest control mats of the present invention, a composition containing natural pyrethrin, one or more phosphorus-based antioxidants selected from the group consisting of diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and a phenolic antioxidant such as BHT.
[0092] One embodiment of the composition for pest control mats of the present invention is a composition containing 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass of a phosphorus-based antioxidant, and 0 to 20 parts by mass, 0.01 to 20 parts by mass, preferably 0 to 10 parts by mass, 0.1 to 10 parts by mass, and more preferably 0 to 5 parts by mass, or 1 to 5 parts by mass of a phenol-based antioxidant such as BHT or 2,2'-methylenebis(6-tert-butyl-4-methylphenol), relative to 13.3 parts by mass of natural pyrethrin.
[0093] Another embodiment of the composition for pest control mats of the present invention is a composition containing 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass of triisodecyl phosphite, and 0 to 30 parts by mass, 0.01 to 30 parts by mass, preferably 0 to 10 parts by mass, 0.1 to 10 parts by mass, and more preferably 0 to 5 parts by mass, or 1 to 5 parts by mass of BHT, relative to 13.3 parts by mass of natural pyrethrin.
[0094] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 10 parts by mass of triisodecyl phosphite, and 0 to 5 parts by mass of BHT.
[0095] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 10 parts by mass of triisodecyl phosphite, and 1 to 5 parts by mass of BHT.
[0096] Another embodiment of the composition for pest control mats of the present invention is a composition containing 1 to 30 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass of diphenylisodecyl phosphite, and 0 to 30 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1 to 8 parts by mass of 2,2'-methylenebis(6-tert-butyl-4-methylphenol), relative to 13.3 parts by mass of natural pyrethrin.
[0097] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 5 parts by mass of diphenylisodecyl phosphite, and 1 to 8 parts by mass of 2,2'-methylenebis(6-tert-butyl-4-methylphenol).
[0098] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 7 to 15 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecylphosphite), and 0 to 30 parts by mass, 0.01 to 30 parts by mass, preferably 0 to 10 parts by mass, 0.1 to 10 parts by mass, and more preferably 0 to 5 parts by mass or 1 to 5 parts by mass of BHT.
[0099] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 7 to 15 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and 0 to 5 parts by mass of BHT.
[0100] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 7 to 15 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and 1 to 5 parts by mass of BHT.
[0101] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and 0 to 30 parts by mass, 0.01 to 30 parts by mass, preferably 0 to 10 parts by mass, 0.1 to 10 parts by mass, and more preferably 0 to 5 parts by mass, or 1 to 5 parts by mass of BHT.
[0102] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 10 parts by mass of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and 0 to 5 parts by mass of BHT.
[0103] Another embodiment of the composition for pest control mats of the present invention is a composition containing 13.3 parts by mass of natural pyrethrin, 1 to 10 parts by mass of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and 1 to 5 parts by mass of BHT.
[0104] In one embodiment of the pest control mat formulation of the present invention, examples of the composition containing natural pyrethrin, a phenolic antioxidant, and a phosphorus-based antioxidant (also referred to as a pest control mat composition) include the following compositions: [Aspect MATB1] A composition containing natural pyrethrin, a phenolic antioxidant, and diphenylisodecyl phosphite. [Aspect MATB2] A composition containing natural pyrethrin, BHT, and diphenylisodecyl phosphite. [Aspect MATB3] A composition containing natural pyrethrin, a phenolic antioxidant, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite). [Aspect MATB4] A composition containing natural pyrethrin, BHT, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite). [Aspect MATB5] A composition containing 28.0 parts by mass of natural pyrethrin (content 47.5%, 13.3 parts by mass as the natural pyrethrin active ingredient), 5 parts by mass of BHT, and 10 parts by mass of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecylphosphite). [Aspect MATB6] A composition containing natural pyrethrin, a phenolic antioxidant, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite. [Aspect MATB7] A composition containing natural pyrethrin, BHT, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite.
[0105] In one embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrins is 1 to 40 w / v%, preferably 5 to 20 w / v%, and more preferably 10 to 15 w / v%, the mass-to-volume concentration of phosphorus-based antioxidant is 1 to 30 w / v%, preferably 1 to 20 w / v%, and more preferably 2 to 10 w / v%, the mass-to-volume concentration of a phenolic antioxidant such as BHT is 0 to 20 w / v%, preferably 0 to 10 w / v%, and more preferably 0 to 5 w / v%, and the content of a solvent such as a paraffin-based solvent is adjusted to the above concentrations, relative to the volume of the pest control mat formulation, wherein the sum of the mass-to-volume concentrations of the natural pyrethrins, the phosphorus-based antioxidant, and the phenolic antioxidant such as BHT does not exceed 100 w / v%.
[0106] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 1 to 40 w / v%, preferably 5 to 20 w / v%, and more preferably 10 to 15 w / v%, relative to the volume of the pest control mat formulation; the mass-to-volume concentration of triisodecyl phosphite is 1 to 30 w / v%, preferably 1 to 20 w / v%, and more preferably 1 to 10 w / v%; the mass-to-volume concentration of BHT is 0 to 30 w / v%, 0.01 to 30 w / v%, preferably 0 to 10 w / v%, 0.1 to 10 w / v%, and more preferably 0 to 5 w / v%, or 1 to 5 w / v%; and the content of paraffinic solvent is adjusted to the above concentrations.
[0107] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of triisodecyl phosphite is 1 to 10 w / v%, the mass-to-volume concentration of BHT is 0 to 5 w / v%, and the content of paraffinic solvent is such that the concentrations are adjusted to the above-mentioned levels, relative to the volume of the pest control mat formulation.
[0108] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of triisodecyl phosphite is 1 to 10 w / v%, the mass-to-volume concentration of BHT is 1 to 5 w / v%, and the content of paraffinic solvent is adjusted to the above concentrations, relative to the volume of the pest control mat formulation.
[0109] In yet another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 1 to 40 w / v%, preferably 5 to 20 w / v%, and more preferably 10 to 15 w / v%, relative to the volume of the pest control mat formulation; the mass-to-volume concentration of diphenylisodecyl phosphite is 1 to 30 w / v%, preferably 1 to 10 w / v%, and more preferably 1 to 5 w / v%; the mass-to-volume concentration of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) is 1 to 30 w / v%, preferably 1 to 10 w / v%, and more preferably 1 to 8 w / v%; and the content of paraffinic solvent is adjusted to the above concentrations.
[0110] In yet another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of diphenylisodecyl phosphite is 1 to 5 w / v%, and the mass-to-volume concentration of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) is 1 to 8 w / v%, relative to the volume of the pest control mat formulation, and the content of paraffinic solvent is such that the concentrations are adjusted to those mentioned above.
[0111] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrins is 1 to 40 w / v%, preferably 5 to 20 w / v%, and more preferably 10 to 15 w / v%, relative to the volume of the pest control mat formulation; the mass-to-volume concentration of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 1 to 30 w / v%, preferably 1 to 20 w / v%, and more preferably 7 to 15 w / v%; the mass-to-volume concentration of BHT is 0 to 30 w / v%, 0.01 to 30 w / v%, preferably 0 to 10 w / v%, 0.1 to 10 w / v%, more preferably 0 to 5 w / v%, or 1 to 5 w / v%, and the content of paraffinic solvent is adjusted to the above concentrations.
[0112] In yet another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 7 to 15 w / v%, the mass-to-volume concentration of BHT is 0 to 5 w / v%, and the content of paraffinic solvent is such that the concentrations are adjusted to those described above, relative to the volume of the pest control mat formulation.
[0113] In yet another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) is 7 to 15 w / v%, the mass-to-volume concentration of BHT is 1 to 5 w / v%, and the content of paraffinic solvent is such that the concentrations are adjusted to those mentioned above, relative to the volume of the pest control mat formulation.
[0114] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 1 to 40 w / v%, preferably 5 to 20 w / v%, and more preferably 10 to 15 w / v%, relative to the volume of the pest control mat formulation; the mass-to-volume concentration of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite is 1 to 30 w / v%, preferably 1 to 20 w / v%, and more preferably 1 to 10 w / v%; the mass-to-volume concentration of BHT is 0 to 30 w / v%, 0.01 to 30 w / v%, preferably 0 to 10 w / v%, 0.1 to 10 w / v%, and more preferably 0 to 5 w / v%, 1 to 5 w / v%; and the content of paraffinic solvent is adjusted to the above concentrations.
[0115] In yet another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite is 1 to 10 w / v%, the mass-to-volume concentration of BHT is 0 to 5 w / v%, and the content of paraffinic solvent is such that the concentrations are adjusted to those described above, relative to the volume of the pest control mat formulation.
[0116] In another embodiment of the pest control mat formulation of the present invention, the mass-to-volume concentration of natural pyrethrin is 10 to 15 w / v%, the mass-to-volume concentration of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite is 1 to 10 w / v%, the mass-to-volume concentration of BHT is 1 to 5 w / v%, and the content of paraffinic solvent is such that the concentrations are adjusted to those mentioned above, relative to the volume of the pest control mat formulation.
[0117] In one embodiment of the pest control mat formulation of the present invention, examples of the pest control mat formulation containing natural pyrethrin, a phenolic antioxidant, and a phosphorus-based antioxidant include the following compositions: [Aspect MATBF1] A pest control mat formulation containing natural pyrethrin, a phenolic antioxidant, diphenylisodecyl phosphite, and a paraffinic solvent. [Aspect MATBF2] A pest control mat formulation containing natural pyrethrin, BHT, diphenylisodecyl phosphite, and a paraffinic solvent. [Aspect MATBF3] A pest control mat formulation containing natural pyrethrin, a phenolic antioxidant, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and a paraffinic solvent. [Aspect MATBF4] A formulation for pest control mats containing natural pyrethrin, BHT, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and a paraffin-based solvent. [Aspect MATBF5] A formulation for pest control mats containing, relative to the volume of the formulation for pest control mats, a mass-to-volume ratio concentration of 28.0 w / v% natural pyrethrin (content 47.5%, 13.3 w / v% as the natural pyrethrin active ingredient), 5 w / v% BHT, and 10 w / v% 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and a paraffin-based solvent in amounts sufficient to adjust to said concentrations. [Aspect MATBF6] A pest control mat formulation containing, relative to the volume of the pest control mat formulation, a mass-to-volume ratio concentration of 28.0 w / v% natural pyrethrin (47.5% content, 13.3 w / v% natural pyrethrin active ingredient), 5 w / v% BHT, 10 w / v% 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecylphosphite), and Isopar M in an amount sufficient to adjust to the above concentrations. [Aspect MATBF7] A pest control mat formulation containing natural pyrethrin, a phenolic antioxidant, tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, and a paraffinic solvent. [Embodiment MATBF8] A formulation for pest control mats containing natural pyrethrin, BHT, tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, and a paraffin-based solvent.
[0118] The pest control mat of one embodiment of the present invention can usually be produced by retaining the formulation for pest control mats of one embodiment of the present invention in a fibrous carrier or a porous carrier by impregnation or the like. Examples of fibrous carriers include natural fibers such as pulp, cellulose, and cotton; synthetic fibers such as polyester and acrylic; and inorganic fibers such as glass fiber and asbestos. Examples of porous carriers include porous inorganic substances such as diatomaceous earth; porous magnetic substances such as unglazed clay; and porous resins such as urethane foam and polypropylene foam. The size of the fibrous carrier or porous carrier used in the present invention is usually 2.0 to 4.0 cm in apparent volume before retaining the formulation for pest control mats. 3 (For example, 2.2 cm x 3.5 cm x 0.28 cm (approximately 2.2 cm 3 ), 3.8cm x 4.8cm x 0.20cm (approximately 3.5cm 3 ) or so), and the pest control mat of one embodiment of the present invention is a fibrous carrier or a porous carrier 2.2 cm 3 The formulation for pest control mats, which is one embodiment of the present invention, can contain other pest control active compounds, repellents, etc. as appropriate, which is expected to further improve efficacy.
[0119] Target pests that are effectively controlled by the pest control mat formulation of one embodiment of the present invention include pests similar to those target pests to which the above-mentioned pest control formulation for thermal vaporization is applied. In particular, mosquitoes such as Culex, Aedes, and Anopheles may also be included as target pests. One embodiment of the present invention is a method for controlling target pests, comprising heating a pest control mat holding a pest control mat formulation to vaporize an effective amount of a pest control mat composition into the atmosphere. Another embodiment of the present invention is a method for controlling target pests, in which the heating of the pest control mat comprises placing the pest control mat on a hot plate and heating the pest control mat with the heated hot plate. Yet another embodiment of the present invention is a method for controlling target pests, in which the heating with the hot plate comprises electrically heating the hot plate to a temperature of approximately 140 to 200°C. In another embodiment of the present invention, the method for controlling target pests is a method for controlling mosquitoes, wherein heating with a hot plate comprises heating the hot plate by burning fuel to a temperature of about 120 to 200° C. In another embodiment of the present invention, the method for controlling target pests is a method for controlling mosquitoes.
[0120] <Resin Formulation> One embodiment of the present invention is a resin formulation containing natural pyrethrins and an antioxidant. The resin formulation of one embodiment of the present invention is a formulation that can be housed in an insect repellent 300, for example, as shown in FIG. 3 . In this specification, a composition containing natural pyrethrins and an antioxidant that is suitable for use in a resin formulation may be referred to as a "resin formulation composition." In the insect repellent 300 of FIG. 3 , a resin formulation 25 formed into a net shape by weaving resin yarns spun from a resin composition containing a thermoplastic resin, natural pyrethrins, and an antioxidant is housed in a housing 20 having openings 23 and 24. The insect repellent 300 can typically be placed in an environment at room temperature (e.g., 5 to 35°C) to volatilize the resin formulation composition contained in the resin formulation 25 into the atmosphere, thereby controlling pests. The housing 20 may be composed of an inner member 21 and an outer member 22, which are movable relative to each other, and when the inner member 21 and the outer member 22 are in a specific position, openings provided in the inner member 21 and the outer member 22 may be separated, sealing the interior of the housing 20. The housing 20 may also be provided with a hook 26 so that the insect repellent can be hung from the hook 26. In another aspect, the resin formulation can control pests that come into contact with the resin formulation. The aspects and methods of use of the resin formulation of one embodiment of the present invention are not limited to those disclosed above; conventionally known resin formulations can also be used, and excellent effects can be achieved in any case. Another embodiment of the present invention is a resin composition for producing the resin formulation. Resin formulations to which the present invention can be applied are described in detail below.
[0121] A resin formulation according to one embodiment of the present invention can be formed by melt-molding a resin composition containing a thermoplastic resin, natural pyrethrins, and an antioxidant. The resin formulation can be produced by melt-spinning the resin composition into resin threads, which are then knitted or woven to form a net-like structure, forming a large number of meshes. In one embodiment of the present invention, the thermoplastic resin is used as a carrier for retaining the natural pyrethrins and antioxidant. Examples of the thermoplastic resin that can be used include polyolefin resins, polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyester, polyamide, polystyrene, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymers, and polyvinyl chloride.
[0122] The thermoplastic resin is preferably a polyolefin-based resin, and the following compounds are preferred as the polyolefin-based resin: (1) α-olefin homopolymers: for example, polyethylene, polypropylene, etc. (2) ethylene-α-olefin copolymers: for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl-1-pentene copolymer, or ethylene-hexene copolymer, etc. (3) Copolymers of ethylene and an organic carboxylic acid derivative having an ethylenically unsaturated bond: for example, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, or ethylene-vinyl acetate-methyl methacrylate copolymer, etc.
[0123] Another embodiment of the present invention is a resin formulation formed by melt-spinning a thermoplastic resin that does not contain a composition for resin formulations containing natural pyrethrins and an antioxidant, knitting or weaving resin threads to form a large number of meshes to form a net, and then coating the net-like molded product with a composition for resin formulations containing natural pyrethrins and an antioxidant. Yet another embodiment of the present invention is a resin formulation formed by melt-spinning a thermoplastic resin composition that contains a thermoplastic resin and either natural pyrethrins or an antioxidant, knitting or weaving resin threads to form a net-like molded product with a large number of meshes to form a net, and then coating the net-like molded product with either natural pyrethrins or an antioxidant that is not contained in the net-like molded product.
[0124] In another embodiment of the present invention, a thermoplastic resin composition containing a thermoplastic resin and a portion of the total amount of the composition for resin formulation containing natural pyrethrins and an antioxidant contained in the final product is melt-spun into resin threads, which are then knitted or woven to form a net so as to form a large number of meshes, and the net-shaped product is then coated with the remaining composition for resin formulation contained in the final product. In yet another embodiment of the present invention, the resin formulation is not limited to a net-shaped product, and may be formed into, for example, a plate, film, sheet (single layer or multilayer), tape, thread, net, cloth, ring, tube, pipe, string, mat, block, or the like.
[0125] In yet another embodiment of the present invention, specific product forms of the resin formulation may be futon covers, pillowcases, protective covers, product packaging, curtains, mattresses, sofa components, animal collars, animal ear tags, clothing, protective hats, arm / leg covers, attracting cords, gardening supports, crop protection films, agricultural mulch, greenhouse films, screen doors, mosquito nets, garbage bags, garbage disposal nets, drainage ditch nets, waste materials, trash cans, drainage materials, cushioning materials, foam materials, heat insulating materials, various tubes, drain pipes, or packing. Regardless of the shape or product form, the resin formulation can exhibit excellent pest control effects by the composition for the resin formulation volatilizing from the resin formulation or by coming into contact with the resin formulation.
[0126] A resin formulation according to one embodiment of the present invention can be produced as follows: (1) A thermoplastic resin, natural pyrethrins, an antioxidant, and optional compounding ingredients are stirred and mixed, and the resulting mixture is melt-kneaded. (2) A thermoplastic resin, at least one component selected from natural pyrethrins and an antioxidant, and optional compounding ingredients are stirred and mixed, and the resulting mixture is melt-kneaded to obtain a resin molded product. The unselected components are then coated onto the surface of the resin molded product. (3) A thermoplastic resin and optional compounding ingredients are stirred and mixed, and the resulting mixture is melt-kneaded to obtain a resin molded product. The natural pyrethrins and antioxidant are then coated onto the surface of the resin molded product. (4) A thermoplastic resin, a portion of the total amount of natural pyrethrins and antioxidants, and optional compounding ingredients are stirred and mixed, and the resulting mixture is melt-kneaded to obtain a resin molded product. The remaining natural pyrethrins and antioxidant are then coated onto the surface of the resin molded product.
[0127] Alternatively, the resin composition of the present invention can be produced by supporting one or more components selected from natural pyrethrins and antioxidants on a carrier and then melt-kneading the resulting support with a thermoplastic resin. Examples of the carrier include silica-based compounds, zeolites, clay minerals, metal oxides, micas, hydrotalcites, and organic carriers. Examples of the silica-based compounds include amorphous silica and crystalline silica, such as powdered silicic acid, finely powdered silicic acid, acid clay, diatomaceous earth, quartz, and white carbon. Zeolites include type A zeolite and mordenite, clay minerals include montmorillonite, saponite, beidellite, bentonite, kaolinite, halloysite, nacrite, dickite, anoxite, illite, and sericite, metal oxides include zinc oxide, magnesium oxide, aluminum oxide, iron oxide, copper oxide, and titanium oxide, micas include mica and vermiculite, hydrotalcites include hydrotalcite and smectite, and organic carriers include charcoal (e.g., charcoal, peat, and grass peat), polymer beads (e.g., microcrystalline cellulose, polystyrene beads, acrylate beads, methacrylate beads, and polyvinyl alcohol beads), and crosslinked polymer beads thereof. Other examples include perlite, gypsum, ceramic, and volcanic rock. Amorphous inorganic carriers are preferred, and amorphous silica is more preferred.
[0128] The resin preparation of one embodiment of the present invention is produced by melt-spinning a resin composition containing a thermoplastic resin, natural pyrethrin, and an antioxidant. In addition, a method commonly used in resin molding can be applied, and the desired molded article can be produced by, for example, extrusion molding, injection molding, blow molding, compression molding, powder molding, press molding, etc. Furthermore, when a molded article is coated with a part of the raw materials, a dipping method, a spraying method, etc. can be applied.
[0129] In one embodiment of the resin formulation of the present invention, the content of the thermoplastic resin is 30 to 99% by mass, preferably 50 to 99% by mass, and the content of the composition for resin formulation containing natural pyrethrins and an antioxidant can be 1 to 70% by mass, preferably 1 to 50% by mass, relative to the total mass of the resin formulation, where the sum of the contents of the thermoplastic resin and the composition for resin formulation does not exceed 100% by mass.
[0130] One embodiment of the composition for resin formulation of the present invention is a composition containing 0.01 to 100 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass of a phosphorus-based antioxidant per 1 part by mass of natural pyrethrin.
[0131] One embodiment of the composition for resin formulation of the present invention is a composition comprising a compound represented by the formula (1) relative to 1 part by mass of natural pyrethrins. [In the formula, R 1 and R 2 has the above-mentioned meaning] in an amount of 0.01 to 100 parts by mass, preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass.
[0132] Another embodiment of the composition for resin formulation of the present invention is a composition containing 0.01 to 100 parts by mass, preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane per part by mass of natural pyrethrin.
[0133] Another embodiment of the composition for resin formulation of the present invention is a composition containing 0.01 to 100 parts by mass, preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass of 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane per part by mass of natural pyrethrin.
[0134] In one embodiment of the composition for resin formulation of the present invention, examples of the composition containing natural pyrethrin and a phosphorus-based antioxidant (also referred to as a composition for resin formulation) include the following compositions. [Aspect R1] A composition containing natural pyrethrin and a compound represented by formula (1). [Aspect R2] A composition containing natural pyrethrin and 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. [Aspect R3] A composition containing 10 parts by mass of natural pyrethrin and 1 part by mass of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. [Aspect R4] A composition containing natural pyrethrin and 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. [Aspect R5] A composition containing 10 parts by weight of natural pyrethrin and 1 part by weight of 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
[0135] Target pests for which the resin formulation of one embodiment of the present invention is effective include pests similar to those for which the above-mentioned pest control formulation for thermal vaporization is applied. In particular, mosquitoes such as Culex, Aedes, and Anopheles can also be listed as target pests. One embodiment of the present invention is a method for controlling target pests, which comprises placing a resin formulation at room temperature and volatilizing an effective amount of a composition for the resin formulation into the atmosphere or contacting target pests with the resin formulation. In another embodiment of the present invention, the method for controlling target pests is a method for exterminating mosquitoes.
[0136] <Manufacturing Use Product> One embodiment of the present invention is a manufacturing use product for producing industrial products such as pest control agents. In this specification, the manufacturing use product may be referred to as a Manufacturing Use Product (hereinafter, may be abbreviated as MUP). MUP is required to be excellent in storage stability by suppressing oxidation and polymerization during storage. The MUP may be a compound selected from the group P pyrethrins and the group P pyrethrins. Uand one or more phosphorus-based antioxidants selected from Group P or one or more sulfur-based antioxidants selected from Group P. UGroup S: a group consisting of pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and didodecyl 3,3'-thiodipropionate. In one embodiment, the MUP may be a composition containing natural pyrethrin and a sulfur-based antioxidant such as pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, or 2,4-bis[(dodecylthio)methyl]-6-methylphenol. In another embodiment, the MUP may further contain a phenol-based antioxidant such as BHT. In yet another embodiment, the MUP may further contain citric acid. In one embodiment, the content of the phosphorus-based antioxidant or sulfur-based antioxidant in the MUP is 0.5 to 12% by mass, 0.5 to 10% by mass, 0.5 to 5% by mass, or 0.5 to 1.5% by mass, preferably 0.8 to 5% by mass, and particularly preferably 0.8 to 1.5% by mass, relative to the total amount of the MUP. The sum of the content of the phosphorus-based antioxidant or sulfur-based antioxidant and the content of natural pyrethrins can be 100% by mass. In another embodiment, when the MUP contains a phenol-based antioxidant such as BHT, the content of BHT is 1 to 10% by mass, preferably 2 to 8% by mass, and particularly preferably 4 to 6% by mass, relative to the total amount of the MUP. The sum of the content of the phosphorus-based antioxidant or sulfur-based antioxidant and the content of natural pyrethrins can be 100% by mass.That is, in the MUP of this embodiment, the content of the phosphorus-based antioxidant or sulfur-based antioxidant is 0.5 to 10 mass%, preferably 0.8 to 5 mass%, and particularly preferably 0.8 to 1.5 mass%, relative to the total amount of MUP; the content of the phenol-based antioxidant such as BHT is 1 to 10 mass%, preferably 2 to 8 mass%, and particularly preferably 4 to 6 mass%, and the sum of the content of the phosphorus-based antioxidant or sulfur-based antioxidant, the content of the phenol-based antioxidant such as BHT, and the content of natural pyrethrins can be 100 mass%. In another embodiment, when the MUP contains citric acid, the content of citric acid is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and particularly preferably 0.8 to 1.5% by mass, relative to the total amount of the MUP, and the sum of the content of the phosphorus-based antioxidant or sulfur-based antioxidant, the content of the phenol-based antioxidant such as BHT, and the content of natural pyrethrins can be 100% by mass.
[0137] One embodiment of the MUP of the present invention is a MUP containing, relative to the total amount of the MUP, a natural pyrethrin content of 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, a phenolic antioxidant content of 0 to 10% by mass, preferably 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, 4,4'-biphenylenediphosphinic acid tetrakis(2,4 the content of one or more antioxidants selected from the group consisting of 3,3'-di-tert-butylphenyl), tridodecyl trithiophosphite, didodecyl 3,3'-thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, and 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.5 to 10 mass%, preferably 0.8 to 5 mass%, and more preferably 0.8 to 1.5 mass%, the content of citric acid is 0 to 10 mass%, 0.5 to 10 mass%, preferably 0.8 to 5 mass%, and more preferably 0.8 to 1.5 mass%, and the sum of the content of natural pyrethrins, the content of phenolic antioxidants such as BHT, the content of the antioxidants, and the content of citric acid does not exceed 100 mass%.
[0138] Another embodiment of the MUP of the present invention is a MUP in which the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass, and the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5 the content of citric acid is 0 to 10 mass%, 0.8 to 10 mass%, preferably 0.8 to 5 mass%, more preferably 0.8 to 1.5 mass%, and the sum of the content of natural pyrethrins, the content of BHT, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the content of citric acid does not exceed 100 mass%.
[0139] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, and the sum of the contents of natural pyrethrins, BHT, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and citric acid does not exceed 100% by mass, relative to the total amount of the MUP.
[0140] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the content of citric acid does not exceed 100% by mass.
[0141] In another embodiment of the MUP of the present invention, the content of natural pyrethrin is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; and the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5% by mass, the content of citric acid is 0 to 10 mass%, 0.8 to 10 mass%, preferably 0.8 to 5 mass%, more preferably 0.8 to 1.5 mass%, and the sum of the content of natural pyrethrins, the content of BHT, the content of 3,3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the content of citric acid does not exceed 100 mass%.
[0142] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrin is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, and the sum of the content of natural pyrethrin, the content of BHT, the content of 3,3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the content of citric acid does not exceed 100% by mass, relative to the total amount of the MUP.
[0143] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, and the sum of the content of natural pyrethrins, the content of BHT, the content of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the content of citric acid does not exceed 100% by mass, relative to the total amount of the MUP.
[0144] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass, the content of tris(nonylphenyl)phosphite is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, and the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, relative to the total amount of the MUP.
[0145] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of tris(nonylphenyl)phosphite is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of tris(nonylphenyl)phosphite, and the content of citric acid does not exceed 100% by mass.
[0146] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of tris(nonylphenyl)phosphite is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of tris(nonylphenyl)phosphite, and the content of citric acid does not exceed 100% by mass.
[0147] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass, the content of triphenyl phosphite is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, and the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, relative to the total amount of the MUP.
[0148] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of triphenyl phosphite is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, triphenyl phosphite, and citric acid does not exceed 100% by mass.
[0149] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of triphenyl phosphite is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, triphenyl phosphite, and citric acid does not exceed 100% by mass.
[0150] In another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; and the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate is 0. The content of citric acid is 0 to 10 mass%, 0.8 to 10 mass%, preferably 0.8 to 5 mass%, more preferably 0.8 to 1.5 mass%, and the sum of the content of natural pyrethrins, the content of BHT, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate, and the content of citric acid does not exceed 100 mass%.
[0151] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, and the sum of the content of natural pyrethrins, the content of BHT, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate, and the content of citric acid does not exceed 100% by mass, relative to the total amount of the MUP.
[0152] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphinate, and the content of citric acid does not exceed 100% by mass.
[0153] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; the content of tridodecyl trithiophosphite is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; and the sum of the contents of natural pyrethrins, BHT, tridodecyl trithiophosphite, and citric acid does not exceed 100% by mass.
[0154] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90 mass%, the content of BHT is 0 to 10 mass%, the content of tridodecyl trithiophosphite is 0.5 to 10 mass%, and the content of citric acid is 0 to 10 mass%, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, tridodecyl trithiophosphite, and citric acid does not exceed 100 mass%.
[0155] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of tridodecyl trithiophosphite is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, tridodecyl trithiophosphite, and citric acid does not exceed 100% by mass.
[0156] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; the content of didodecyl 3,3'-thiodipropionate is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; and the sum of the content of natural pyrethrins, the content of BHT, the content of didodecyl 3,3'-thiodipropionate, and the content of citric acid does not exceed 100% by mass.
[0157] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of didodecyl 3,3'-thiodipropionate is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of didodecyl 3,3'-thiodipropionate, and the content of citric acid does not exceed 100% by mass.
[0158] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of didodecyl 3,3'-thiodipropionate is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of didodecyl 3,3'-thiodipropionate, and the content of citric acid does not exceed 100% by mass.
[0159] In another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; and the content of pentaerythritol tetrakis[3-(dodecylthio)propionate] is 0. The content of citric acid is 0 to 10 mass%, 0.8 to 10 mass%, preferably 0.8 to 5 mass%, more preferably 0.8 to 1.5 mass%, and the sum of the content of natural pyrethrins, the content of BHT, the content of pentaerythritol tetrakis[3-(dodecylthio)propionate], and the content of citric acid does not exceed 100 mass%.
[0160] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of pentaerythritol tetrakis[3-(dodecylthio)propionate] is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, pentaerythritol tetrakis[3-(dodecylthio)propionate], and citric acid does not exceed 100% by mass.
[0161] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of pentaerythritol tetrakis[3-(dodecylthio)propionate] is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, pentaerythritol tetrakis[3-(dodecylthio)propionate], and citric acid does not exceed 100% by mass.
[0162] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass, the content of 2-mercaptobenzimidazole is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, and the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass, relative to the total amount of the MUP.
[0163] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of 2-mercaptobenzimidazole is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, 2-mercaptobenzimidazole, and citric acid does not exceed 100% by mass.
[0164] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of 2-mercaptobenzimidazole is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the contents of natural pyrethrins, BHT, 2-mercaptobenzimidazole, and citric acid does not exceed 100% by mass.
[0165] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, preferably 30 to 80% by mass, 50 to 80% by mass, and more preferably 50 to 75% by mass, relative to the total amount of the MUP; the content of BHT is 0 to 10% by mass, 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 6% by mass; the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.5 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; the content of citric acid is 0 to 10% by mass, 0.8 to 10% by mass, preferably 0.8 to 5% by mass, and more preferably 0.8 to 1.5% by mass; and the sum of the content of natural pyrethrins, the content of BHT, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and the content of citric acid does not exceed 100% by mass.
[0166] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 0 to 10% by mass, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.5 to 10% by mass, and the content of citric acid is 0 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and the content of citric acid does not exceed 100% by mass.
[0167] In yet another embodiment of the MUP of the present invention, the content of natural pyrethrins is 20 to 90% by mass, the content of BHT is 1 to 10% by mass, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol is 0.5 to 10% by mass, and the content of citric acid is 0.8 to 10% by mass, relative to the total amount of the MUP, and the sum of the content of natural pyrethrins, the content of BHT, the content of 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and the content of citric acid does not exceed 100% by mass.
[0168] The composition of the present invention can also be applied in the agricultural field. The composition of the present invention can be mixed or used in combination with one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d) below (hereinafter referred to as the present component). The term "mixed or used in combination" means that the composition of the present invention and the present component are used simultaneously, separately, or with a time interval between them. When the composition of the present invention and the present component are used simultaneously, the composition of the present invention and the present component may be contained in separate formulations or in a single formulation. In one embodiment of the present invention, although not particularly limited, the one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d) below are mixed or used in combination in an amount of 0.001 to 1,000 parts by mass, preferably 0.002 to 500 parts by mass, and more preferably 0.01 to 100 parts by mass per part by mass of natural pyrethrins. One aspect of the present invention is a composition (hereinafter referred to as Composition A) containing one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d), and the composition of the present invention. One embodiment of Composition A is not particularly limited, but is a composition containing 0.001 to 1,000 parts by mass, preferably 0.002 to 500 parts by mass, and more preferably 0.01 to 100 parts by mass of one or more components selected from the group consisting of Group (a), Group (b), Group (c), and Group (d) below, per part by mass of natural pyrethrins:
[0169] Group (a) includes acetylcholinesterase inhibitors (e.g., carbamate insecticides, organophosphate insecticides), GABAergic chloride channel blockers (e.g., phenylpyrazole insecticides), sodium channel modulators (e.g., pyrethroid insecticides), nicotinic acetylcholine receptor competitive modulators (e.g., neonicotinoid insecticides), nicotinic acetylcholine receptor allosteric modulators, glutamate-gated chloride channel allosteric modulators (e.g., macrolide insecticides), juvenile hormone mimics, multisite inhibitors, chordotonal organ TRPV channel modulators, mite growth inhibitors, microbial insect midgut membrane disruptors, mitochondrial ATP synthase inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers (e.g., nereistoxin insecticides), chitin biosynthesis inhibitors, molting inhibitors, ecdysone receptor agonists, octopamine receptor agonists, mitochondrial electron transport chain complexes I and II, The group consisting of inhibitors of classes III and IV, voltage-dependent sodium channel blockers, acetyl-CoA carboxylase inhibitors, ryanodine receptor modulators (e.g., diamide insecticides), chordotonal organ modulators, microbial insecticides, and other insecticidal, acaricidal, and nematicidal active ingredients, which are described in the IRAC mechanism-based classification.
[0170] Group (b) consists of nucleic acid synthesis inhibitors (e.g., phenylamide fungicides, acylamino acid fungicides), cell division and cytoskeleton inhibitors (e.g., MBC fungicides), respiratory inhibitors (e.g., QoI fungicides, QiI fungicides), amino acid synthesis and protein synthesis inhibitors (e.g., anilinopyridine fungicides), signal transduction inhibitors, lipid synthesis and membrane synthesis inhibitors, sterol biosynthesis inhibitors (e.g., DMI fungicides such as triazoles), cell wall biosynthesis inhibitors, melanin synthesis inhibitors, plant defense inducers, multisite contact-active fungicides, microbial fungicides, and other fungicidal active ingredients. These are listed in the FRAC classification based on the mechanism of action.
[0171] Group (c) is a group of plant growth regulators (including mycorrhizal fungi and rhizobia).
[0172] Group (d) is a group of repellent ingredients.
[0173] The composition of the present invention is effective against harmful arthropods such as harmful insects and harmful mites, harmful nematodes, and harmful mollusks. Examples of harmful arthropods, harmful nematodes, and harmful mollusks include the following:
[0174] Hemiptera: Small brown planthopper (Laodelphax striatellus), Brown planthopper (Nilaparvata lugens), White-backed planthopper (Sogatella furcifera), Corn planthopper (Peregrinus maidis), Yellow leafhopper (Javesella pellucida), Black horned planthopper (Perkinsiella saccharicida), Tagosodes orizicolus, Stenocranus pacificus and other Delphacidae; Green rice leafhopper (Nephotettix cincticeps), Taiwan green rice leafhopper (Nephotettix virescens), Black-striped green rice leafhopper (Nephotettix nigropictus), Lightning leafhopper (Recilia dorsalis), Tea green leafhopper (Empoasca Cicadellidae, such as the potato leafhopper (Empoasca fabae), the corn leafhopper (Dalbulus maidis), the white giant leafhopper (Cofana spectra), and Amrasca biguttula biguttula; Aphrophoridae, such as the European spittlebug (Philaenus spumarius); Cercopidae, such as Mahanarva posticata and Mahanarva fimbriolata;Black bean aphid (Aphis fabae), soybean aphid (Aphis glycines), cotton aphid (Aphis gossypii), European apple aphid (Aphis pomi), willow aphid (Aphis spiraecola), green peach aphid (Myzus persicae), strawberry aphid (Brachycaudus helichrysi), radish aphid (Brevicoryne brassicae), rosy apple aphid (Dysaphis plantaginea), false radish aphid (Lipaphis erysimi), tulip aphid (Macrosiphum euphorbiae), potato aphid (Aulacorthum solani), lettuce aphid (Nasonovia ribisnigri), wheat collar aphid (Rhopalosiphum padi), corn aphid (Rhopalosiphum maidis), citrus black aphid (Toxoptera citricida), peach butterbur aphid (Hyalopterus pruni), barnyard millet aphid (Melanaphis sacchari), Japanese black aphid (Tetraneura nigriabdominalis), cotton aphid (Ceratovacuna lanigera), apple aphid (Eriosoma lanigerum), English grain aphid (Sitobion avenae), etc. Aphididae; grape aphid (Daktulosphaira vitifoliae), pecan phylloxera (Phylloxera devastatrix), pecan leaf phylloxera (Phylloxera notabilis), southern pecan leaf phylloxera (Phylloxera Phylloxeridae, such as (Russelae);Adelgidae, such as the Japanese hemlock aphid (Adelges tsugae), the balsam woolly aphid (Adelges piceae), and the small brown aphid (Aphrastasia pectinatae); Scotinophara lurida, Scotinophara coarctata, Nezara antennata, Eysarcoris aeneus, Eysarcoris lewisi, Eysarcoris ventralis, Eysarcoris annamita, Halyomorpha halys, and Nezara Pentatomidae, such as the brown stink bug (Euschistus heros), the red-banded stink bug (Piezodorus guildinii), Oebalus pugnax, Dichelops melacanthus, and the spotted stink bug (Piezodorus hybneri); Cydnidae, such as the narrow-banded stink bug (Riptortus clavatus), the spider stink bug (Leptocorisa chinensis), and the narrow-banded stink bug (Leptocorisa acuta); Cletus punctiger, Leptoglossus Coreidae, such as Cavelerius saccharivorus, Togo hemipterus, and Blissus leucopterus; Lygaeidae, such as Cavelerius saccharivorus, Togo hemipterus, and Blissus leucopterus;Miridae (Miridae) such as the red-bearded green rice bug (Trigonotylus caelestialium), the red-striped rice bug (Stenotus rubrovittatus), the long-spined wheat rice bug (Stenodema calcarata), and the rusty rice bug (Lygus lineolaris); Aleyrodidae (Aleyrodidae) such as the greenhouse whitefly (Trialeurodes vaporariorum), the tobacco whitefly (Bemisia tabaci), the citrus whitefly (Dialeurodes citri), the citrus spine whitefly (Aleurocanthus spiniferus), the tea spine whitefly (Aleurocanthus camelliae), and the Japanese oak leaf butterflies (Pealius euryae); cyanophylli), red scale (Aonidiella aurantii), pear scale (Diaspidiotus perniciosus), mulberry scale (Pseudaulacaspis pentagona), Yanon scale (Unaspis yanonensis), false Yanon scale (Unaspis citri) and other scale insects (Diaspididae); Coccidae such as ruby scale (Ceroplastes rubens); Margarodidae such as Icerya purchasi and yellow cotton scale (Icerya seychellarum);Pseudococcidae, such as the eggplant mealybug (Phenacoccus solani), the sable mealybug (Phenacoccus solenopsis), the wisteria mealybug (Planococcus kraunhiae), the mulberry mealybug (Pseudococcus comstocki), the citrus mealybug (Planococcus citri), the moth mealybug (Pseudococcus calceolariae), the long-legged mealybug (Pseudococcus longispinus), and the tuttlemey bug (Brevennia rehi); the citrus psyllid (Diaphorina citri), the citrus psyllid (Trioza erytreae), the pear psyllid (Cacopsylla pyrisuga), and the Chinese pear psyllid (Cacopsylla Psyllidae, such as the Japanese chinensis, the potato psyllid (Bactericera cockerelli), and the cacopsylla (Cacopsylla pyricola); Tingidae, such as the plane tree earworm (Corythucha ciliata), the goldenrod earworm (Corythucha marmorata), the Japanese pear earworm (Stephanitis nashi), and the azalea earworm (Stephanitis pyrioides); Cimicidae, such as the bedbug (Cimex lectularius) and the netted whitefly (Cimex hemipterus); Cicadidae, such as the Quesada gigas; Triatoma infestans, Triatoma rubrofasciata, and Triatoma Reduviidae, such as the Venezuelan assassin bug (Rhodonius prolixus);
[0175] Lepidoptera: Chilo suppressalis, Dark-headed stem borer, Chilo polychrysus, White stem borer, Scirpophaga innotata, Scirpophaga incertulas, Rupela albina, Rice leaf borer, Cnaphalocrocis medinalis, Marasmia patnalis, Rice casino borer, Marasmia exigua, Cotton borer, Notarcha derogata, European corn borer, Ostrinia furnacalis, European corn borer, Hellula undalis, Black-spotted corn borer, Herpetogramma luctuosale, Rice stalk moth, Nymphula Crambidae, such as the Japanese corn moth (Elasmopalpus lignosellus), the Indian meal moth (Plodia interpunctella), the Japanese two-spotted moth (Euzophera batangensis), and the Japanese striped moth (Cadra cautella);Common cutworm (Spodoptera litura), beet armyworm (Spodoptera exigua), armyworm (Mythimna separata), armyworm (Mamestra brassicae), rice armyworm (Sesamia inferens), white armyworm (Spodoptera mauritia), two-banded cutworm (Naranga aenescens), leaf fall armyworm (Spodoptera frugiperda), African armyworm (Spodoptera exempta), Spodoptera cosmioides, semi-tropical armyworm (Spodoptera eridania), red cutworm (Agrotis ipsilon), turnip cutworm (Agrotis segetum), red rice looper (Autographa nigrisigna), rice yellow looper (Plusia festucae), soybean Heliothis spp. such as the cotton bollworm (Chrysodeixis includens), Trichoplusia spp., and Heliothis spp. such as the false tobacco budworm (Heliothis virescens), Helicoverpa spp. such as the cotton bollworm (Helicoverpa armigera) and the corn earworm (Helicoverpa zea), Noctuidae such as the velvet bean caterpillar (Anticarsia gemmatalis), the cotton leafworm (Alabama argillacea), and the hop wine borer (Hydraecia immanis); Pieridae such as the cabbage white butterfly (Pieris rapae);Pear fruit moth (Grapholita molesta), plum fruit moth (Grapholita dimorpha), bean fruit moth (Leguminivora glycinivorella), adzuki bean pea moth (Matsumuraeses azukivora), apple smaller tortrix (Adoxophyes orana fasciata), tea smaller tortrix (Adoxophyes honmai), tea tortrix (Homona magnanima), green tea tortrix (Archips fuscocupreanus), codling moth (Cydia pomonella), citrus fruit borer (Tetramoera schistaceana), bean shoot borer (Epinotia aporema), citrus fruit borer (Citripestis sagittiferella), European grape wine moth (Lobesia Tortricidae such as Caloptilia theivora and Phyllonorycter ringoniella; Gracilariae such as Carposinidae; Leucoptera coffeella, Lyonetiidae such as Lyonetia clerkella, Lyonetia prunifoliella; Lymantria spp. such as Lymantria dispar, Euproctis spp. such as Euproctis pseudoconspersa; Plutella xylostella Plutellidae, such as Plutellidae (Plutella xylostella);Gelechiidae (Gelechiidae) such as the peach leaf moth (Anarsia lineatella), the potato leaf moth (Helcystogramma triannulella), the red bollworm moth (Pectinophora gossypiella), the potato tuber moth (Pthorimaea operculella), and the tomato leaf moth (Tuta absoluta); Arctiidae (Arctiidae) such as the American fall webworm (Hyphantria cunea); Castniidae (Castniidae) such as the giant sugarcane borer (Telchin licus); Cossidae (Cossidae) such as the small box moth (Cossus insularis); Geometridae (Geometridae) such as the mugwort geometrid (Ascotis selenaria); Parasa Limacodidae such as Stathmopodidae (Stathmopoda masinissa) and the like; Sphingidae such as Acherontia lachesis (Sphingidae); Sesiidae such as Nokona feralis (Nokona feralis), Synanthedon hector (Synanthedon tenuis) and the like; Hesperiidae such as Parnara guttata (Parnara guttata); Tineidae such as Tinea translucens (Tineola bisselliella) and the like.
[0176] Thysanoptera: Thripidae such as Frankliniella occidentalis, Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, Stenchaetothrips biformis, Echinothrips americanus, and Scirtothrips perseae; Phlaeothripidae such as Haplothrips aculeatus.
[0177] Diptera: Anthomyiidae such as Delia platura, Delia antiqua, and Pegomya cunicularia; Ulidiidae such as Tetanops myopaeformis; Agromyzidae such as Agromyza oryzae, Liriomyza sativae, Liriomyza trifolii, and Chromatomyia horticola; Chloropidae such as Chlorops oryzae; Bactrocera Tephritidae, such as the Oriental fruit fly (Bactrocera dorsalis), the eggplant fly (Bactrocera latifrons), the olive fruit fly (Bactrocera oleae), the Queensland fruit fly (Bactrocera tryoni), the Mediterranean fruit fly (Ceratitis capitata), the apple maggot (Rhagoletis pomonella), and the cherry fruit fly (Rhacochlaena japonica); Ephydridae, such as the rice leafminer (Hydrellia griseola), the Asian rice leafminer (Hydrellia philippina), and the rice leafminer (Hydrellia sasakii); Drosophila suzukii Drosophilidae, such as Drosophila melanogaster (Drosophila suzukii) and Drosophila melanogaster; Phoridae, such as Megaselia spiracularis; Psychodidae, such as Clogmia albipunctata;Sciaridae (Sciaridae) such as Bradysia difformis and Bradysia odoriphaga; Cecidomyiidae (Cecidomyiidae) such as Mayetiola destructor and Orseolia oryzae; Diopsidae (Diopsis macrophthalma); Glossinidae (Tsetse flies) such as Glossina palpalis and Glossina morsitans; Simuliidae (Simuliidae) such as Simulium japonicum and Simulium damnosum; Phlebotominae (Phlebotominae); Tipula aino (Craned fly), Tipula oleracea (Common crane fly), and Tipula Tipulidae such as Culex pipiens pallens, Culex tritaeniorhynchus, Culex pipiens f. molestus, Culex quinquefasciatus, Culex pipiens pipiens, Culex vishnui, Aedes albopictus, Aedes aegypti, Anopheles sinensis, Anopheles gambiae, Anopheles stephensi, Anopheles coluzzii, Anopheles albimanus, Anopheles sundaicus, Anopheles mosquito family (Culicidae) such as arabiensis, Anopheles funestus, Anopheles darlingi, Anopheles farauti, Anopheles minimus;Simulidae (Family Simuliidae) such as Prosimulium yezoensis and Simulium ornatum; Tabanidae (Family Tabanus trigonus) and other such flies; Muscidae (Family Musca domestica), Muscina stabulans, Stomoxys calcitrans, Haematobia irritans and other such flies; Calliphoridae (Family Sarcophagidae); Chironomidae (Family Chironomidae) such as Chironomus plumosus, Chironomus yoshimatsui, Glyptotendipes tokunagai and other such flies; Fannidae (Family Fannidae);
[0178] Coleoptera: Diabrotica spp. (e.g., Western corn rootworm (Diabrotica virgifera virgifera), Southern corn rootworm (Diabrotica undecimpunctata howardi), Northern corn rootworm (Diabrotica barberi), Mexican corn rootworm (Diabrotica virgifera zeae), Banded cucumber beetle (Diabrotica balteata), Cucumber beetle (Diabrotica speciosa), etc.), Bean leaf beetle (Cerotoma trifurcata), Red-necked leaf beetle (Oulema melanopus), Cucumber leaf beetle (Aulacophora femoralis), Striped flea beetle (Phyllotreta striolata), Cabbage leaf beetle (Phyllotreta cruciferae), Western black leaf beetle (Phyllotreta pusilla, cabbage stem beetle (Psylliodes chrysocephala), hop beetle (Psylliodes punctulata), Colorado potato beetle (Leptinotarsa decemlineata), rice leaf beetle (Oulema oryzae), grape colaspis (Colaspis brunnea), corn beetle (Chaetocnema pulicaria), sweet potato leaf beetle (Chaetocnema confinis), potato beetle (Epitrix cucumeris), rice spur beetle (Dicladispa armigera), southern corn leaf beetle (Myochrous denticollis), four-spotted tortoise beetle (Laccoptera quadrimaculata), tobacco flea beetle (Epitrix hirtipennis), radish leaf beetle (Phaedon Chrysomelidae, such as the two-striped leaf beetle (Medythia nigrobilineata);Carabidae beetles such as the seed corn beetle (Stenolophus lecontei) and the slender seed corn beetle (Clivina impressifrons); Phyllophaga spp. such as the cuprea beetle (Anomala cuprea), the rufocuprea beetle (Anomala rufocuprea), the green beetle (Anomala albopilosa), the Japanese beetle (Popillia japonica), the long-legged beetle (Heptophylla picea), the European chafer (Rhizotrogus majalis), the black marsh beetle (Tomarus gibbosus), the black beetle (Holotrichia spp.), and the June beetle (Phyllophaga crinita); Diloboderus spp. such as Diloboderus abderus. Scarabaeidae (Scarabaeidae) such as Araecerus coffeae (Boll weevil); Anthriibidae (Anthriibidae) such as Cylas formicarius (Sweet potato weevil); Bruchidae (Brachiidae) such as Zabrotes subfasciatus (Brazilian bean weevil); Scolytidae (Scolytidae) such as Tomicus piniperda (Pine bark beetle), Hypothenemus hampei (Coffee berry borer);Potato weevil (Euscepes postfasciatus), alfalfa weevil (Hypera postica), maize weevil (Sitophilus zeamais), rice weevil (Sitophilus oryzae), granaria weevil (Sitophilus granarius), rice weevil (Echinocnemus squameus), rice water weevil (Lissorhoptrus oryzophilus), white grain weevil (Rhabdoscelus lineaticollis), boll weevil (Anthonomus grandis), grass band weevil (Sphenophorus venatus), southern cornbill bug (Sphenophorus callosus), soybean stalk weevil (Sternechus subsignatus), sugarcane weevil (Sphenophorus levis), rust gourd weevil (Scepticus The Aracanthus spp. (Aracanthus spp.) such as Aracanthus griseus, Scepticus uniformis, Aracanthus mourei, and the cotton root borer (Eutinobothrus brasiliensis) are also included in the Curculionidae family; the Tenebrionidae (Tenebrionidae) such as Tribolium castaneum, Tribolium confusum, and Alphitobius diaperinus are also included in the Coccinellidae family; the Flat-headed Ladybird (Lyctus brunneus), the Rhizopertha dominica); Ptinidae; Cerambycidae, such as Anoplophora malasiaca, Migdolus fryanus, and Aromia bungii;Elateridae beetles such as the Okinawan wireworm beetle (Melanotus okinawensis), the brown-headed wireworm beetle (Agriotes fuscicollis), the comb beetle (Melanotus legatus), the foot-striped wireworm beetle (Anchastus spp.), the Conoderus spp., the Ctenicera spp., the Limonius spp., and the Aeolus spp.; Staphylinidae beetles such as the blue-leaf rove beetle (Paederus fuscipes); the small-leaved weevils (Anthrenus verbasci) and the white-striped weevils (Dermestes Dermestidae such as Trogoderma granarium (Trogoderma maculates) and the like; Anobiidae such as Lasioderma serricorne (tobacco beetle) and Stegobium paniceum (Anobiidae); Laemophloeidae such as Cryptolestes ferrugineus (Laemophloeidae); Silvanidae such as Oryzaephilus surinamensis (Silvanidae); Nitidulidae such as Brassicogethes aeneus (Blossom beetle).
[0179] Orthoptera: Migratory locust (Locusta migratoria), Moroccan locust (Dociostaurus maroccanus), Australian locust (Chortoicetes terminifera), Red locust (Nomadacris septemfasciata), Brown locust (Locustana pardalina), Tree locust (Anacridium melanorhodon), Italian locust (Calliptamus italicus), Differential grasshopper (Melanoplus differentialis), Two-striped grasshopper (Melanoplus bivittatus), Migratory grasshopper (Melanoplus sanguinipes), Red-legged grasshopper (Melanoplus femurrubrum), Clear-winged grasshopper (Camnula pellucida), Desert grasshopper (Schistocerca The grasshoppers (Acrididae) include the common locust (Oxya gregaria), yellow-winged locust (Gastrimargus musicus), sparse-throated locust (Austracris guttulosa), oriental grasshopper (Oxya yezoensis), long-winged locust (Oxya japonica), and Taiwan grasshopper (Patanga succincta); the grasshoppers (Gryllotalpidae) include the common house cricket (Gryllotalpa orientalis); the crickets (Gryllidae) include the European house cricket (Acheta domestica) and the field cricket (Teleogryllus emma); and the katydids (Tettigoniidae) include the Mormon cricket (Anabrus simplex).
[0180] Hymenoptera: Tenthredinidae such as Athalia rosae and Athalia japonica; Solenopsis spp. such as Solenopsis invicta and Solenopsis geminata, Atta spp. such as Atta capiguara, Acromyrmex spp., Paraponera clavata, Ochetellus glaber, Monomorium pharaonis, Linepithema humile, Formica japonica, Pristomyrmex punctutus, Pheidole Camponotus spp. such as Camponotus noda, Pheidole megacephala, Camponotus japonicus, Camponotus obscuripes, Pogonomyrmex spp. such as Pogonomyrmex occidentalis, Wasmania spp. such as Wasmania auropunctata, Formicidae such as Anoplolepis gracilipes; Vespa mandarinia, Vespa simillima, Vespa analis, Vespa Vespidae, such as Polistes velutina and Polistes jokahamae; Siricidae, such as Urocerus gigas; and Bethylidae.
[0181] Blattodea: Ectobiidae, such as the German cockroach (Blattella germanica); Blattidae, such as the American cockroach (Periplaneta fuliginosa), the American cockroach (Periplaneta americana), the American cockroach (Periplaneta australasiae), the brown cockroach (Periplaneta brunnea), and the Asian cockroach (Blatta orientalis); Reticulitermes speratus, Coptotermes formosanus, Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanus, and Neotermes Termites of the family Termitidae, such as the Satsuma termite (Glyptotermes satsumensis), Nakajima termite (Glyptotermes nakajimai), Katan termite (Glyptotermes fuscus), Hodotermopsis sjostedti, Koshu termite (Coptotermes guangzhouensis), Amami termite (Reticulitermes amamianus), Miyatake termite (Reticulitermes miyatakei), Formosan termite (Reticulitermes kanmonensis), Takasago termite (Nasutitermes takasagoensis), Snocapritermes nitobei, Sinocapritermes mushae, and Cornitermes cumulans.
[0182] Order Siphonaptera: Family Pulicidae such as human flea (Pulex irritans), cat flea (Ctenocephalides felis), dog flea (Ctenocephalides canis), rat flea (Xenopsylla cheopis), chicken flea (Echidnophaga gallinacea), etc.; Family Hectopsyllidae such as sand flea (Tunga penetrans); Family Ceratophyllidae such as European rat flea (Nosopsyllus fasciatus).
[0183] Psocodae: Pediculidae, such as head louse (Pediculus humanus capitis); Pthiridae, such as pubic louse (Pthirus pubis); Haematopinidae, such as cow louse (Haematopinus eurysternus) and pig louse (Haematopinus suis); Linognathidae, such as cow louse (Linognathus vituli), sheep trunk louse (Linognathus ovillus), and woolly cow louse (Solenopotes capillatus); Bovicola bovis, sheep louse (Bovicola ovis), Bovicola breviceps, Damalinia Bovicoliidae, such as Trichodectes canis and Felicola subrostratus; Menoponidae, such as Menopon gallinae, Menacanthus stramineus, and Trinoton spp.; Trimenoponidae, such as Cummingsia spp.; Trogiidae, such as Trogium pulsatorium; Liposcelis corrodens and Liposcelis Liposcelidae or Liposcelididae, such as Liposcelis bostrychophila, Liposcelis pearmani, and Liposcelis entomophila.
[0184] Thysanura: Family Lepismatidae, including the Japanese silverfish (Ctenolepisma villosa) and the European silverfish (Lepisma saccharina).
[0185] Acari: Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Tetranychus evansi, Panonychus citri, Panonychus ulmi, Oligonychus spp.; Aculops pelekassi, Aculops citri, Aculops lycopersici, Calacarus carinatus, Acaphylla theavagrans, Eriophyes chibaensis, Aculops spp. Eriophyidae such as Aceria diospyri, Aceria tosichella, and Shevtchenkella sp.; Tarsonemidae such as Polyphagotarsonemus latus; Tenuipalpidae such as Brevipalpus phoenicis; Tuckerellidae;Haemaphysalis longicornis, Haemaphysalis flava, Haemaphysalis japonica, Haemaphysalis campanulata, Dermacentor variabilis, Dermacentor taiwanensis, Rocky Mountain wood tick (Dermacentor andersoni), Dermacentor reticulatus, Ixodes ovatus, Ixodes persulcatus, Black-legged tick (Ixodes scapularis), Western black-legged tick (Ixodes pacificus), Ixodes holocyclus, Ixodes ricinus, Lone star tick (Amblyomma Ixodidae ticks such as Amblyomma americanum, Amblyomma maculatum, Rhipicephalus microplus, Rhipicephalus annulatus, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, and Rhipicephalus decoloratus; Argasidae ticks such as Argas persicus, Ornithodoros hermsi, and Ornithodoros turicata; Acaridae ticks such as Tyrophagus putrescentiae and Tyrophagus similis; Dermatophagoides farinae and Dermatophagoides pteronyssinus. Pyroglyphidae, such as Pteronyssinus;Cheyletidae such as Cheyletus eruditus, Cheyletus malaccensis, Chelacaropsis moorei, and Cheyletiella yasguri; Psoroptidae such as Psoroptes ovis, Psoroptes equi, Knemidocoptes mutans, Otodectes cynotis, and Chorioptes spp.; Notoedres cati, Notoedres muris, and Sarcoptes Sarcoptidae such as (Scabiei); Listrophoridae such as (Listrophorus gibbus); Dermanyssidae such as (Dermanyssus gallinae); Macronyssidae such as (Ornithonyssus sylviarum) and (Ornithonyssus bacoti); Varroa destructor such as (Varroa jacobsoni); Demodicidae such as (Demodex canis) and (Demodex cati); Leptotrombidium akamushi and (Leptotrombidium Trombiculidae, such as Leptotrombidium scutellare, Leptotrombidium pallidum, and Leptotrombidium scutellare.
[0186] Araneae: Eutichuridae, such as Cheiracanthium japonicum; Theridiidae, such as Latrodectus hasseltii. Polydesmida: Paradoxosomatidae, such as Oxidus gracilis and Nedyopus tambanus. Isopoda: Armadillidiidae, such as Armadillidium vulgare. Chilopoda: Scutigeridae such as Thereuonema hilgendorfi; Scolopendridae such as Scolopendra subspinipes; Ethopolyidae such as Bothropolys rugosus. Class Gastropoda: Family Limacidae such as the brown slug (Limax marginatus) and the yellow slug (Limax flavus); Family Philomycidae such as the slug (Meghimatium bilineatum); Family Ampullariidae such as the apple snail (Pomacea canaliculata); Family Lymnaeidae such as the lymnae snail (Austropeplea ollula).
[0187] Nematoda: Aphelenchoididae, such as the rice root-lesion nematode (Aphelenchoides besseyi); Pratylenchidae, such as Pratylenchus coffeae, Pratylenchus brachyurus, Pratylenchus neglectus, and Radopholus similis; Meloidogyne javanica, Meloidogyne incognita, guava root-knot nematodes (Meloidogyne enterolobii), Meloidogyne hapla, soybean cyst nematode (Heterodera glycines), potato cyst nematode (Globodera Heteroderidae such as Globodera rostochiensis, potato white cyst nematode (Globodera pallida), and Colombian root-knot nematode (Meloidogyne chitwoodi); Hoplolaimidae such as Rotylenchulus reniformis; Anguinidae such as Nothotylenchus acris and Ditylenchus dipsaci; Tylenchulidae such as Tylenchulus semipenetrans; Longidoridae such as Xiphinema index; Trichodoridae; Parasitaphelenchidae such as Bursaphelenchus xylophilus.
[0188] The harmful insects, harmful arthropods such as harmful mites, harmful mollusks, and harmful nematodes may be harmful insects, harmful arthropods such as harmful mites, harmful mollusks, and harmful nematodes that have reduced sensitivity to insecticides, acaricides, molluscicides, or nematocides, or that have developed resistance to the insecticides, acaricides, molluscicides, or nematocides.
[0189] The method for controlling arthropod pests of the present invention is carried out by applying an effective amount of the composition of the present invention or composition A directly to the arthropod pests and / or to the habitat of the arthropod pests (plants, soil, houses, animals, etc.). Examples of the method for controlling arthropod pests of the present invention include foliage treatment, soil treatment, root treatment, shower treatment, fumigation treatment, water surface treatment, and seed treatment.
[0190] The composition of the present invention or composition A is typically prepared by mixing an inactivated carrier such as a solid carrier, liquid carrier, or gaseous carrier with a surfactant or the like, and optionally adding formulation adjuvants such as binders, dispersants, and stabilizers to prepare formulations such as aqueous suspensions, oil suspensions, oil solutions, emulsifiable concentrates, emulsion formulations, microemulsions, microcapsule formulations, wettable powders, water dispersible granules, dusts, granules, tablets, aerosols, and resin formulations. The composition of the present invention or composition A can be formulated into any dosage form, including those described in the Manual on development and use of FAO and WHO Specifications for pesticides, FAO Plant Production and Protection Papers-271 to 276, prepared by the FAO / WHO Joint Meeting on Pesticide Specifications, 2016, ISSN:0259-2517. These formulations typically contain 0.0001 to 99% by weight of the composition of the present invention or composition A.
[0191] Examples of solid carriers include clay (pyrophyllite clay, kaolin clay, etc.), talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acid clay, attapulgite, white carbon, ammonium sulfate, vermiculite, perlite, pumice, silica sand, fine powder and granular chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), and resins (polyethylene, polypropylene, polyester, polyurethane, polyamide, polyvinyl chloride, etc.).
[0192] Examples of liquid carriers include water, alcohols (ethanol, cyclohexanol, benzyl alcohol, propylene glycol, polyethylene glycol, etc.), ketones (acetone, cyclohexanone, etc.), aromatic hydrocarbons (xylene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), esters (ethyl acetate, methyl oleate, propylene carbonate, etc.), nitriles (acetonitrile, etc.), ethers (ethylene glycol dimethyl ether, etc.), amides (N,N-dimethylformamide, N,N-dimethyloctanamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), lactams (N-methylpyrrolidone, N-octylpyrrolidone, etc.), fatty acids (oleic acid, etc.), and vegetable oils (soybean oil, etc.).
[0193] Examples of gaseous carriers include fluorocarbons, butane gas, LPG (liquefied petroleum gas), dimethyl ether, nitrogen, and carbon dioxide gas.
[0194] Examples of surfactants include nonionic surfactants (polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyethylene glycol fatty acid esters, etc.) and anionic surfactants (alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, etc.).
[0195] Other formulation adjuvants include binders, dispersants, colorants, stabilizers, etc., and specific examples include polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), acid isopropyl phosphate, and dibutylhydroxytoluene.
[0196] Adjuvants can also be used as ingredients that enhance or support the efficacy of active ingredients. Specific examples include Nimbus (registered trademark), Assist (registered trademark), Aureo (registered trademark), Iharol (registered trademark), Silwet L-77 (registered trademark), BreakThru (registered trademark), Sundance II (registered trademark), Induce (registered trademark), Penetrator (registered trademark), AgriDex (registered trademark), Lutensol A8 (registered trademark), NP-7 (registered trademark), Triton (registered trademark), Nufilm (registered trademark), Emulgator NP7 (registered trademark), Emulad (registered trademark), TRITON X 45 (registered trademark), AGRAL 90 (registered trademark), AGROTIN (registered trademark), ARPON (registered trademark), EnSpray N (registered trademark), and BANOLE (registered trademark).
[0197] In the present invention, the plant includes the whole plant, stems and leaves, flowers, spikes, fruits, trunks, branches, crowns, seeds, vegetative reproductive organs, and seedlings.
[0198] Vegetative reproductive organs refer to plant roots, stems, leaves, and other parts that can grow when separated from the main body and placed in soil. Examples of vegetative reproductive organs include tuberous roots, creeping roots, bulbs, corms (or solid bulbs), tubers, rhizomes, stolons, rhizophores, cane cuttings, propagules, and vine cuttings. Stolons are sometimes called runners, and propagules are also called bulbils and are divided into broad buds and bulbils. Vines refer to shoots (a collective term for leaves and stems) of plants such as sweet potatoes and Japanese yams. Bulbs, corms, tubers, rhizomes, stem fragments, rhizophores, and tuberous roots are collectively called bulbils. Potato cultivation begins by planting tubers in the soil, and the tubers used are generally called seed potatoes.
[0199] Examples of methods for controlling harmful arthropods by applying an effective amount of the composition of the present invention or composition A to soil include methods of applying an effective amount of the composition of the present invention or composition A to soil before or after planting plants. More specifically, for example, planting hole treatment (spraying in planting holes, mixing in soil for planting hole treatment), root treatment (spraying in planting holes, mixing in soil for planting holes, irrigation in planting holes, root treatment in the latter half of the seedling raising period), planting furrow treatment (spraying in planting furrows, mixing in soil for planting furrows), row treatment (row spraying, mixing in soil for row, row spraying in the growing season), row treatment at sowing (row spraying at sowing, mixing in soil for row at sowing), overall treatment (overall soil spraying, overall soil mixing), side row treatment, water surface treatment (water surface application, water surface application after flooding), other soil spray treatments (foliar spraying of granules during the growing season, spraying under the crown or around the main trunk, soil surface spraying, soil surface mixing, seeding hole spraying, furrow surface spraying, spraying between plants), and others. Other irrigation treatments include soil irrigation, seedling irrigation, chemical injection treatment, ground level irrigation, chemical drip irrigation, chemigation), seedling tray treatments (seedling tray spraying, seedling tray irrigation, seedling tray flooding), seedling tray treatments (seedling tray spraying, seedling tray irrigation, seedling tray flooding), seedling bed treatments (seedling bed spraying, seedling bed irrigation, water seedling bed spraying, seedling immersion), bed soil mixing treatments (bed soil mixing, bed soil mixing before sowing, spraying before soil covering at sowing, spraying after soil covering at sowing, covering soil mixing), and other treatments (hilling soil mixing, plowing in, topsoil mixing, rain-drop soil mixing, planting position treatment, granular inflorescence spraying, paste fertilizer mixing).
[0200] Seed treatments include, for example, treatment of seeds or vegetative reproductive organs with the composition of the present invention or Composition A. More specifically, examples include spray treatments in which a suspension of the composition of the present invention or Composition A is sprayed onto the surface of seeds or vegetative reproductive organs; smear treatments in which the composition of the present invention or Composition A is applied to seeds or vegetative reproductive organs; immersion treatments in which seeds or vegetative reproductive organs are immersed in a solution of the composition of the present invention or Composition A for a certain period of time; and methods of coating seeds or vegetative reproductive organs with a carrier containing the composition of the present invention or Composition A (film coating treatment, pellet coating treatment, etc.). Seed potatoes are particularly examples of such vegetative reproductive organs. When applying Composition A to seeds or vegetative reproductive organs, Composition A can be applied to the seeds or vegetative reproductive organs as a single formulation, or different formulations of Composition A can be applied to the seeds or vegetative reproductive organs in multiple separate applications. Examples of methods for treating seeds or vegetative reproductive organs with multiple different formulations of Composition A include a method of treating the seeds or vegetative reproductive organs with a formulation containing only the composition of the present invention as an active ingredient, air-drying the seeds or vegetative reproductive organs, and then treating them with a formulation containing this ingredient; and a method of treating the seeds or vegetative reproductive organs with a formulation containing both the composition of the present invention and this ingredient as active ingredients, air-drying the seeds or vegetative reproductive organs, and then treating them with a formulation containing a component other than the component already treated. In the present invention, "seeds or vegetative reproductive organs bearing the composition of the present invention or Composition A" refers to seeds or vegetative reproductive organs to which the composition of the present invention or Composition A is attached. The seeds or vegetative reproductive organs bearing the composition of the present invention or Composition A may have materials other than the composition of the present invention or Composition A attached to them before or after the composition of the present invention or Composition A is attached to the seeds or vegetative reproductive organs. Furthermore, when Composition A is attached to the surface of the seeds or vegetative reproductive organs in layers, the layers may consist of one layer or multiple layers. Furthermore, when the composition consists of multiple layers, each layer may contain one or more active ingredients, or may consist of a layer containing one or more active ingredients and a layer containing no active ingredients. Seeds or vegetative reproductive organs carrying the composition of the present invention or composition A can be obtained, for example, by applying a formulation containing the composition of the present invention or composition A to the seeds or vegetative reproductive organs by the seed treatment method described above.
[0201] When the composition of the present invention or composition A is used for controlling harmful arthropods in the agricultural field, the application amount is 10,000 m 2 The amount of the composition of the present invention is usually 1 to 10,000 g per kg of seed or vegetative reproductive organ. When treating seeds or vegetative reproductive organs, the amount of the composition of the present invention is usually applied in the range of 0.001 to 100 g per kg of seed or vegetative reproductive organ. When the composition of the present invention or Composition A is formulated as an emulsifiable concentrate, wettable powder, flowable powder, or the like, it is usually applied after being diluted with water to a concentration of the active ingredient of 0.01 to 10,000 ppm, and granules, dusts, and the like are usually applied as is.
[0202] The composition of the present invention or composition A can also be applied by wrapping the resin preparation in the form of a sheet or string around the crop, stretching it near the crop, or spreading it on the soil around the base of the plant.
[0203] When the composition of the present invention or composition A is used to control harmful arthropods living in houses, the application amount is 1 / 2 m for a treatment area of 1 m when applied to a surface. 2 The amount of the composition of the present invention per square meter is usually 0.01 to 1,000 mg. When treating in a space, the amount is usually 0.01 to 1,000 mg per square meter of treatment space. 3 When the composition of the present invention or composition A is formulated as an emulsifiable concentrate, wettable powder, flowable powder or the like, it is usually applied after diluting with water to a concentration of the active ingredient of 0.1 to 10,000 ppm, whereas oil solutions, aerosols, fumigants, poison baits and the like are applied as is.
[0204] When the composition of the present invention or composition A is used to control ectoparasites in livestock such as cattle, horses, pigs, sheep, goats, and chickens, or small animals such as dogs, cats, rats, and mice, it can be administered to animals using methods known in veterinary medicine. Specific methods of administration include, for example, administration by tablet, incorporation into feed, suppository, or injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) for systemic control, and administration by methods such as spraying an oil or aqueous liquid, pour-on application, spot-on application, washing the animal with a shampoo formulation, or attaching a resin formulation to the animal as a collar or ear tag. When administered to an animal, the amount of the composition of the present invention or composition A is typically in the range of 0.1 to 1,000 mg per kg of the animal's body weight.
[0205] The composition of the present invention or composition A can be used as an agent for controlling harmful arthropods in agricultural lands such as fields, paddy fields, lawns, orchards, etc. Examples of plants include the following.
[0206] Corn (horse-tooth, hard grain, soft grain, explosive, glutinous, sweet, field corn), rice (long grain, short grain, medium grain, japonica, tropical japonica, indica, javanica, paddy rice, upland rice, floating rice, direct-seeded rice, transplanted rice, glutinous rice), wheat (bread wheat (hard, soft, medium, red wheat, white wheat), durum wheat, spelt wheat, club wheat, each winter wheat type, spring wheat type), barley (two-row barley (= beer barley), six-row barley, naked barley, waxy barley, each winter barley type, spring barley type), rye (winter rye type, spring rye type), triticale (winter triticale type, spring triticale type), oats (winter oat type, spring oat type), sorghum, cotton (upland type, pima type), soybean (fully harvested seed varieties, edamame varieties, green-harvested varieties, indeterminate, determinate, semi-determinate types), peanuts, buckwheat, sugar beet (sugar production, animal feed, root vegetable, leafy vegetable, fuel), rapeseed (winter rapeseed type, spring rapeseed type), canola (winter canola type, spring canola type), sunflower (oil production, food, ornamental), sugarcane, tobacco, tea plant, mulberry, solanaceous vegetables (eggplant, tomato, bell pepper, chili pepper) , potatoes, etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), Cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard greens, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garland chrysanthemum, artichoke, lettuce, etc.), Liliaceae vegetables (leeks, onions, garlic, asparagus, etc.), Umbelliferae vegetables (carrots, parsley, celery, parsley, etc.), Chenopodiaceae vegetables (spinach, Swiss chard, etc.), Lamiaceae vegetables (perilla, mint, basil, etc.), strawberries, sweet potatoes, yams, scallions, Sweet potatoes, pome fruits (apples, European pears, Japanese pears, Chinese pears, quince, quince, etc.), stone fruits (peaches, plums, nectarines, plums, cherries, apricots, prunes, etc.), citrus fruits (Satsuma mandarins, oranges, lemons, limes, grapefruits, etc.), nuts (chestnuts, walnuts, hazelnuts, almonds, pistachios, cashew nuts, macadamia nuts, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, figs, olives, loquats, bananas, coffee, dates, coconuts, ornamental plants, forest plants,Turfgrass, pasture grass,
[0207] The above-mentioned plants are not particularly limited as long as they are varieties that are commonly cultivated, and include plants that can be produced by natural crossbreeding, plants that can be generated by mutation, F1 hybrid plants, and genetically modified crops. Examples of genetically modified crops include plants that have been conferred resistance to herbicides such as HPPD (4-hydroxyphenylpyruvate dioxygenase enzyme) inhibitors such as isoxaflutole, ALS (acetolactate synthase) inhibitors such as imazethapyr and thifensulfuron methyl, EPSP (5-enolpyruvylshikimate-3-phosphate synthase) inhibitors, glutamine synthetase inhibitors, PPO (protoporphyrinogen oxidase) inhibitors, bromoxynil, or dicamba; plants that are capable of synthesizing selective toxins known to be found in the genus Bacillus, such as Bacillus thuringiensis; and plants that can be conferred specific insecticidal activity by synthesizing gene fragments that partially match endogenous genes derived from harmful insects and inducing gene silencing (RNAi; RNA interference) in the target harmful insect.
[0208] The present invention will be described in more detail below with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these Examples. The following antioxidants were used in the Examples and Comparative Examples.Antioxidant 1: 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) (JPH-1200 (manufactured by Johoku Chemical Industry Co., Ltd.)); Antioxidant 2: diphenylisodecyl phosphite (ADK STAB 135A (manufactured by ADEKA)); Antioxidant 3: 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (JPE-13R (manufactured by Johoku Chemical Industry Co., Ltd.)); Antioxidant 4: 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (JPE-10 (manufactured by Johoku Chemical Industry Co., Ltd.)); Antioxidant 5: bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Revonox 608 (manufactured by Chitec Technology)); Antioxidant 6: 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADK STAB PEP24 (manufactured by ADEKA)); Antioxidant 7: tris(nonylphenyl) phosphite (JP-351 (manufactured by Johoku Chemical Industry Co., Ltd.)); Antioxidant 8: triphenyl phosphite (triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.)); Antioxidant 9: 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl) (HOSTANOX (trademark) P-EPQ (trademark) (Clariant Chemicals)); Antioxidant 10: tridodecyl trithiophosphite (JPS-312 (Johoku Chemical Industry)); Antioxidant 11: 3,3'-thiodipropionate didodecyl (Tokyo Chemical Industry); Antioxidant 12: pentaerythritol tetrakis[3-(dodecylthio)propionate] (Sumilizer (trademark) TP-D (Sumitomo Chemical)); Antioxidant 13: 2-mercaptobenzimidazole (Tokyo Chemical Industry); Antioxidant 14: 2,4-bis[(dodecylthio)methyl]-6-methylphenol (Irganox™ 1726 (manufactured by BASF Japan)); Antioxidant 15: triisodecyl phosphite (ADK STAB 3010 (manufactured by ADEKA)); Antioxidant 16: tetra(C12-15 alkyl)-4,4′-isopropylidenediphenyl diphosphite (ADK STAB 1500 (manufactured by ADEKA)).
[0209] Example 1 (thermal evaporation pest control formulation 1) 1.26 parts by mass of natural pyrethrin (content 47.5%, 0.6 parts by mass of natural pyrethrin active ingredient), 5 parts by mass of BHT, and 2 parts by mass of triisodecyl phosphite were mixed with 91.74 parts by mass of Isopar G (manufactured by ExxonMobil Corporation) to make a total of 100 parts by mass, to obtain thermal evaporation pest control formulation 1.
[0210] Example 1-2 (Pest control formulation 2 for thermal evaporation) Pest control formulation 2 for thermal evaporation was obtained by mixing 1.26 parts by mass of natural pyrethrin (content 47.5%, 0.6 parts by mass of the natural pyrethrin active ingredient), 5 parts by mass of BHT, and 0.5 parts by mass of triisodecyl phosphite with 93.24 parts by mass of a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L (Isopar M (trade name) and Isopar L (trade name) are both manufactured by ExxonMobil Corporation) to make a total of 100 parts by mass.
[0211] Comparative Example 9 (Comparative Pest Control Formulation for Heat-Transpiration) 1.26 parts by mass of natural pyrethrin (content 47.5%, 0.6 parts by mass of natural pyrethrin active ingredient) was mixed with 98.74 parts by mass of Isopar G (manufactured by ExxonMobil Corporation) to make a total of 100 parts by mass, to obtain a comparative pest control formulation for heat-transpiration.
[0212] Examples 2 and 3, Comparative Examples 1 and 2 (Production of pest control mat formulations and pest control mats) Pest control mat formulations were produced by mixing the components to obtain the compositions shown in Table 1. 0.75 mL of the produced pest control mat formulation was spread on blank mat material (made of pulp and cotton linter, thickness 0.21 cm, long side 3.5 cm, short side 2.2 cm) to obtain pest control mats each containing 100 mg of natural pyrethrin as an active ingredient (in Comparative Example 1, a pest control mat each containing 200 mg of natural pyrethrin as an active ingredient was obtained).
[0213] In the table, phenolic antioxidant 1 is BHT; phenolic antioxidant 2 is 2,2′-methylenebis(6-t-butyl-4-methylphenol) (Sumilizer (trademark) MDP-S (manufactured by Sumitomo Chemical)); the co-solvent is isopropyl myristate; and the solvent is an isoparaffin-based solvent (Isopar M (trade name), manufactured by ExxonMobil Corporation).
[0214] Examples 4 and 5, Comparative Example 3 (Production of Composition for Resin Formulation) Each component was mixed so as to obtain the composition shown in Table 2, to produce a composition for resin formulation.
[0215]
[0216] Examples 6 to 25 and Comparative Examples 4 and 5 (Production of MUP) The MUPs of Examples 6 to 15 were produced by mixing 500 mg of natural pyrethrins (75% content (375 mg of natural pyrethrin active ingredient), 5% (25 mg) of BHT), 5 mg of an antioxidant shown in Table 3, and 5 mg of citric acid so as to achieve the composition shown in Table 3. The MUPs of Examples 16 to 25 were produced by mixing 500 mg of natural pyrethrins (75% content (375 mg of natural pyrethrin active ingredient), 5% (25 mg) of BHT) and 5 mg of an antioxidant shown in Table 3 so as to achieve the composition shown in Table 3. The MUP of Comparative Example 4 was also produced by mixing 500 mg of natural pyrethrins (75% content (375 mg of natural pyrethrin active ingredient), 5% (25 mg) of BHT) and 5 mg of citric acid. Comparative Example 5 contains 500 mg of the natural pyrethrins used in the Examples (containing 75% of the natural pyrethrins (375 mg of the active ingredient amount), and 5% of BHT (25 mg)).
[0217]
[0218] Examples 26 to 29 (Production of pest control formulations for thermal evaporation) Natural pyrethrin (content 47.5% (0.6% by mass as the amount of the natural pyrethrin active ingredient), 5.0% by mass of BHT, 0.5% by mass or 0.25% by mass of an antioxidant shown in Table 4, and 15% by mass of diisopropyl adipate were mixed to obtain the compositions shown in Table 4, and then mixed with a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L to produce the pest control formulations for thermal evaporation of Examples 26 to 29.
[0219] In the table, auxiliary solvent 2 is diisopropyl adipate; and the solvent used was an isoparaffinic solvent, a mixed solvent of Isopar M and Isopar L in a 4:6 (weight ratio) mixture (Isopar M (trade name) and Isopar L (trade name) are both manufactured by ExxonMobil Corporation).
[0220] Reference Example 1 (Production of a pest control formulation for thermal evaporation) Natural pyrethrin (content 47.5% (0.6% by mass as the amount of the natural pyrethrin active ingredient)) and 5.0% by mass of BHT were mixed, and then mixed with a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L to produce the pest control formulation for thermal evaporation of Reference Example 1.
[0221] Reference Example 2 (Production of a pest control formulation for thermal evaporation) Natural pyrethrin (content 47.5% (0.6% by mass as the amount of the natural pyrethrin active ingredient)) and 0.5% by mass of BHT were mixed, and then mixed with a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L to produce the pest control formulation for thermal evaporation of Reference Example 2.
[0222] Examples 30 to 35 and Comparative Example 6 (Production of pest control formulations for thermal evaporation) Natural pyrethrin (content 47.5% (0.6% by mass as the amount of the natural pyrethrin active ingredient), 0.5% by mass of BHT (1.0% by mass in Comparative Example 6), and 0.5% by mass of an antioxidant shown in Table 5 were mixed to obtain the compositions shown in Table 5, and then mixed with a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L to produce pest control formulations for thermal evaporation of Examples 30 to 35 and Comparative Example 6.
[0223] In the table, the solvent used was an isoparaffinic solvent, a 4:6 (weight ratio) mixed solvent of Isopar M and Isopar L (both Isopar M (trade name) and Isopar L (trade name) are manufactured by ExxonMobil Corporation).
[0224] Examples 36 to 45 (Preparation of Compositions Containing Natural Pyrethrins) Natural pyrethrins (content 47.5% (200 mg of the active ingredient of natural pyrethrins)) and 150 mg of an antioxidant shown in Table 6 were mixed on an aluminum dish (diameter 3.8 cm) to prepare the natural pyrethrin-containing compositions of Examples 36 to 45.
[0225]
[0226] Comparative Example 7 (Preparation of a composition containing natural pyrethrin) Natural pyrethrin (content 47.5% (200 mg of active natural pyrethrin)) was placed on an aluminum dish (diameter 3.8 cm) to prepare a composition of Comparative Example 7.
[0227] Comparative Example 8 (Preparation of a composition containing natural pyrethrin) Natural pyrethrin (content 47.5% (200 mg of the active ingredient of natural pyrethrin)) and 150 mg of BHT were mixed on an aluminum dish (diameter 3.8 cm) to prepare a composition of Comparative Example 8.
[0228] Test Example 1 (Evaluation of Pest Control Formulations for Thermal Transpirability (Clay Core)) 34 g of Pest Control Formulation 1 for Thermal Transpirability obtained in Example 1 or 34 g of Pest Control Formulation 2 for Thermal Transpirability obtained in Example 1-2 was filled into a 45 mL plastic container, and a porous liquid-absorbent wick (7 mm in diameter, 73 mm in length, made of fired silica, calcite, etc. (clay)) was inserted through an inner stopper so that the top could be heated with a heater to obtain a bottle containing Pest Control Formulation 1 for Thermal Transpirability with a liquid-absorbent wick or a bottle containing Pest Control Formulation 2 for Thermal Transpirability with a liquid-absorbent wick. The bottle was placed in the thermal transpirability insecticide device shown in Figure 1 and heated at a heater temperature of 140°C. The heating method consisted of 8 hours of continuous heating followed by 16 hours of stopping the heating, which was defined as one cycle (1 day), and this was repeated. In specific cycles from the start of heating to 58 cycles (58 days), the amount of natural pyrethrin volatilized for 1 hour was measured 4 to 5 hours after the start of heating. The test was performed twice, and the amount of natural pyrethrins evaporated was calculated as the average of the two measurements. The amount of natural pyrethrins evaporated was determined by collecting the evaporated natural pyrethrins over time in a glass column packed with polyurethane sponge as an adsorbent, extracting the polyurethane sponge with acetone, and quantitatively analyzing the amount of natural pyrethrins using high performance liquid chromatography (absolute calibration curve method). The results are shown in Table 7.
[0229] In the table, ND means that the value was not measured. The pest control formulations for thermal evaporation of Examples 1 and 1-2 contain specific amounts of specific antioxidants, and therefore have excellent volatilization amounts of natural pyrethrins per hour, which can be maintained for a long period of time.
[0230] Quantitation of natural pyrethrins by high-performance liquid chromatography can be carried out, for example, under the analytical conditions described in "Separation and quantitative analysis of natural pyrethrins by high-performance liquid chromatography," Chromatographia, 1999, Vol. 50, pp. 607-610.
[0231] Test Example 2 (Evaluation of formulations for pest control mats) Two pest control mats (total amount of natural pyrethrin active ingredient: 200 mg / treatment area) prepared in Examples 2 and 3 and Comparative Examples 1 and 2 were heated on a ceramic heater at 180°C, and the amount of natural pyrethrin volatilized for one hour between 3 and 4 hours after the start of heating was analyzed. The results are shown in Table 8.
[0232] The pest control mat formulations of Examples 2 and 3 contain a specific amount of a specific antioxidant, and therefore have a superior amount of natural pyrethrin volatilization in one hour between 3 and 4 hours after the start of heating compared to Comparative Examples 1 and 2.
[0233] Test Example 3 (Evaluation of Compositions for Resin Formulations) Natural pyrethrins and the antioxidants used in Examples 6, 7, and Comparative Example 3 were each dissolved in an appropriate amount of acetone, and then the solution was dropped into a 4.5 cm diameter Petri dish so that the natural pyrethrins were 0.3 mg and the antioxidants used in Examples 6, 7, and Comparative Example 3 were 0.03 mg. The solution was then spread evenly and allowed to dry for 5 days to obtain a composition of the present invention. The Petri dish was placed in a plastic cup, the lid was closed, and 10 adult female mosquitoes were released. The number of knocked-down insects after the "KD evaluation time" listed in Table 6 was counted to determine the knock-down rate. The knock-down rate (hereinafter referred to as "KD rate") can be calculated using the following formula: KD rate (%) = (number of knocked-down insects / number of test insects) × 100. The results are shown in Table 9.
[0234] The compositions for resin formulations of Examples 4 and 5 contain a specific amount of a specific antioxidant, and therefore have a superior knockdown rate of pests after a predetermined time has elapsed compared to Comparative Example 3.
[0235] Test Example 4 (Evaluation of MUP) The MUP solutions of Examples 6 to 25 and Comparative Examples 4 and 5 were placed in 2 mL glass containers, and the glass containers were set in a block heater heated to 90°C. The block heater was covered with aluminum foil to shield the glass containers from light, and the containers were heated at 90°C for 14 days to obtain samples. The obtained samples were removed from the glass containers and dissolved in tetrahydrofuran (THF), and the amount of polymer component contained in the samples was measured according to the following analytical conditions. The Munsell values of the samples were also determined according to the following appearance observation method.
[0236] Analysis conditions High performance liquid chromatography (GPC) Pump: Shimadzu Corporation LC-20A Detector: Shimadzu Corporation RID-20A differential refractive index detector Column: Tosoh Corporation TSKgel G5000HHR (7.8 x 300 mm) x 2 (in series) Guard column: Tosoh Corporation TSKgel G5000HHR (6.0 x 40 mm) Column temperature: 40°C Eluent: tetrahydrofuran Flow rate: 1 mL / min
[0237] Appearance Observation Method: The above sample heated at 90°C for 14 days was transferred to a glass container with a diameter of 1 cm without adding THF, and visually observed from the side against a white background and compared with the Munsell standard color chart. The results are shown in Table 10.
[0238] The MUPs of Examples 6 to 25 contain specific amounts of specific antioxidants, and as a result, the increase in the amount of polymer components after storage at 90°C for 14 days while heating is suppressed compared to Comparative Examples 4 and 5. In other words, the storage stability is improved. Furthermore, MUPs containing citric acid tend to have the above-mentioned effects more excellently than MUPs that do not contain citric acid. Furthermore, it has been confirmed that some antioxidants contain specific amounts of specific antioxidants, which are effective in suppressing deterioration of appearance, such as coloration.
[0239] Test Example 5 (Evaluation of Thermally Transpirable Pest Control Formulations (Ceramic Wicks)) 34 g of the thermally transpirable pest control formulations obtained in Examples 26 to 29 were filled into 45 mL plastic containers, and a porous liquid-absorbent wick (7 mm diameter, 73 mm length, ceramic) was inserted through an inner stopper so that the top could be heated with a heater to prepare a bottle containing a thermally transpirable pest control formulation with a liquid-absorbent wick. The bottle was placed in the thermally transpirable insecticide device shown in Figure 1 and heated at a heater temperature of 140°C. The heating method consisted of 8 hours of continuous heating followed by 4 hours of stopping heating, which was defined as one cycle, and this cycle was repeated. In specific cycles from the start of heating to the 44th cycle, the amount of natural pyrethrin volatilized for 1 hour, 4 to 5 hours after the start of heating, was measured. The test was performed in duplicate, and the amount of natural pyrethrin volatilized was calculated as the average of the two measurements. The amount of evaporated natural pyrethrins was determined by collecting evaporated natural pyrethrins over time in a glass column packed with polyurethane sponge as an adsorbent, extracting the polyurethane sponge with acetone, and quantitatively analyzing the amount of natural pyrethrins by high performance liquid chromatography (absolute calibration curve method). The results are shown in Table 11.
[0240]
[0241] Test Example 6 (Evaluation 2 of Pest Control Formulations for Thermal Transpirability (Ceramic Core)) 34 g of the pest control formulations for thermal transpirability obtained in Examples 30 to 35 and Comparative Example 6 were filled into 45 mL plastic containers, and a porous liquid-absorbent wick (diameter 7 mm, length 73 mm, ceramic) was inserted through an inner stopper so that the top could be heated with a heater to obtain a bottle containing a pest control formulation for thermal transpirability with a liquid-absorbent wick. The bottle was placed in the thermal transpirability insecticide device shown in Figure 1 and heated at a heater temperature of 140 ° C. The heating method consisted of 8 hours of continuous heating followed by 4 hours of stopping the heating, which was considered one cycle, and this was repeated. After 20 cycles from the start of heating (total heating time 160 hours), the molecular weight (polystyrene equivalent) of the polymer formed in the heated portion of the porous liquid-absorbent wick was determined by high-performance liquid chromatography (GPC) using the method described in Polymer Analysis Conditions.
[0242] [Polymer analysis condition 1] High performance liquid chromatography (GPC) Pump: Shimadzu Corporation LC-20AD Detector: Shimadzu Corporation Photodiode array detector SPD-M20A Detection wavelength: 254 nm Column: Shimadzu Corporation Shim-pack GPC-803 (8.0 mm ID x 300 mm), Shimadzu Corporation Shim-pack GPC-804 (8.0 mm ID x 300 mm) (in series) Guard column: Shimadzu Corporation GPC-800P (4.6 x 10 mm) Column temperature: 40°C Eluent: tetrahydrofuran Flow rate: 1 mL / min
[0243] The results are shown in Table 12.
[0244]
[0245] Test Example 7 (Evaluation of Natural Pyrethrin-Containing Compositions) Aluminum dishes containing the natural pyrethrin-containing compositions obtained in Examples 36 to 45 and Comparative Examples 7 and 8 were heated on a ceramic heater at 180°C for 1 hour. The molecular weight (in terms of polystyrene) of the polymer formed on the aluminum dish was determined by high performance liquid chromatography (GPC) using the method described under polymer analysis conditions. The results are shown in Table 13.
[0246]
[0247] Test Example 8 (Evaluation of Pest Control Formulation for Thermal Transpirability) 45 mL of the pest control formulation for thermal transpirability 1 obtained in Example 1 was filled into a 45 mL plastic container, and a porous liquid-absorbing wick (diameter 7 mm, length 73 mm, fired silica and calcite, etc. (made of china clay)) was inserted through an inner stopper so that the top could be heated with a heater to obtain a bottle containing the pest control formulation for thermal transpirability 1 for thermal transpirability. The bottle was placed in the thermal transpirability insecticide device of FIG. 1 and heated at a heater temperature of 140 ° C. The heating method consisted of 8 hours of continuous heating followed by 16 hours of stopping the heating, which was defined as one cycle (1 day), and this was repeated. In a specific cycle from the start of heating to 60 cycles (60 days), the KD rate in that cycle (after the cumulative number of days of use had elapsed) was determined by the following method. Twenty adult female Culex pipiens pallens (Culex pipiens pallens) were placed in a 4.5 cm diameter, 12 cm tall glass tube, and 16-mesh nylon netting was secured to the top and bottom openings of the tube with rubber bands to enclose the mosquitoes. A 22 cm diameter, 83 cm tall metal tube was placed upright, and two glass tubes containing the mosquitoes were secured to the top openings. The bottles were placed in the thermal evaporation insecticide device shown in Figure 1, placed in the bottom opening of the metal tube, and heated at a heater temperature of 140°C. After 30 minutes, the number of knocked-down Culex pipiens mosquitoes was recorded to determine the knock-down rate (hereinafter referred to as the KD rate). The KD rate can be calculated using the following formula: KD rate (%) = (number of knocked-down insects / number of test insects) × 100. The test was performed in duplicate, and the KD rate was calculated as the average of the two replicates. The results are shown in Table 14.
[0248]
[0249] According to the present invention, a novel composition containing natural pyrethrins can be provided, which maintains its pest control effect and has excellent storage stability.
[0250] REFERENCE SIGNS LIST 1 Solution containing composition for thermal evaporation 2 Heating body 3 Absorbent wick 4 Chemical solution bottle 10 Hot plate 11 Pest control mat 12 Power switch 13 Housing 20 Housing 21 Inner member 22 Outer member 23, 24 Opening 25 Resin preparation 26 Hook
Claims
1. A composition containing natural pyrethrin and one or more phosphorus-based antioxidants selected from Group P or one or more sulfur-based antioxidants selected from Group S: Group P: Formula (1) [In the formula, R 1 and R 2 and are the same or different and represent a C9-C14 alkyl group.], the group consisting of 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, tridodecyl trithiophosphite, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecylphosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyldiphosphite; Group S: A group consisting of pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, and didodecyl 3,3′-thiodipropionate.
2. Group P is 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl), trithiophosphite tridodecyl, triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl) 2. The composition of claim 1, wherein the aryl group is the group consisting of tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, ditridecyl phosphite, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite.
3. The composition according to claim 1 or 2, which contains a phenolic antioxidant.
4. One or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group S are selected from group P L The composition according to claim 1, which is one or more phosphorus-based antioxidants selected from the group P L The group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, and 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite).
5. The composition of claim 4, further comprising a phenolic antioxidant.
6. A pest control formulation for thermal evaporation comprising the composition according to claim 4 and a paraffin-based solvent.
7. A method for exterminating mosquitoes using the composition according to claim 4 or 5 or the pest control formulation for thermal evaporation according to claim 6.
8. One or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group S are selected from group P M The composition according to claim 1, which is one or more phosphorus-based antioxidants selected from the group P M The group consisting of triisodecyl phosphite, diphenylisodecyl phosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), and tetra(C12-15 alkyl)-4,4'-isopropylidene diphenyl diphosphite.
9. The composition of claim 8, further comprising a phenolic antioxidant.
10. The composition according to claim 1, wherein the one or more phosphorus-based antioxidants selected from group P or the one or more sulfur-based antioxidants selected from group S are compounds represented by formula (1).
11. The composition according to claim 1, wherein the one or more phosphorus-based antioxidants selected from group P or the one or more sulfur-based antioxidants selected from group S are 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane or 3,9-bis(isotridecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
12. One or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group S are selected from group P. U The composition according to claim 1, wherein the antioxidant is one or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group P. U The group consisting of 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, and tridodecyl trithiophosphite.
13. One or more phosphorus-based antioxidants selected from group P or one or more sulfur-based antioxidants selected from group S are selected from group P U The composition according to claim 12, wherein the phosphorus-based antioxidant is one or more selected from the group consisting of:
14. The composition according to claim 12, wherein the one or more phosphorus-based antioxidants selected from group P or the one or more sulfur-based antioxidants selected from group S are one or more sulfur-based antioxidants selected from group S.
15. The composition according to claim 14, wherein the one or more sulfur-based antioxidants selected from group S are pentaerythritol tetrakis[3-(dodecylthio)propionate], 2-mercaptobenzimidazole, or 2,4-bis[(dodecylthio)methyl]-6-methylphenol.
16. The composition according to any one of claims 12 to 15, further comprising a phenolic antioxidant.
17. The composition according to any one of claims 12 to 15, which contains citric acid.
18. The composition of claim 16, further comprising citric acid.
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