WO2020179617A1 - One-liquid-type aqueous aerosol composition - Google Patents

One-liquid-type aqueous aerosol composition Download PDF

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Publication number
WO2020179617A1
WO2020179617A1 PCT/JP2020/008040 JP2020008040W WO2020179617A1 WO 2020179617 A1 WO2020179617 A1 WO 2020179617A1 JP 2020008040 W JP2020008040 W JP 2020008040W WO 2020179617 A1 WO2020179617 A1 WO 2020179617A1
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Prior art keywords
aerosol composition
aqueous aerosol
surfactant
aerosol
component aqueous
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PCT/JP2020/008040
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French (fr)
Japanese (ja)
Inventor
敬範 山城
洋子 小林
中山　幸治
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大日本除蟲菊株式会社
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Priority to CN202080018619.9A priority Critical patent/CN113518556A/en
Publication of WO2020179617A1 publication Critical patent/WO2020179617A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M7/00—Special adaptations or arrangements of liquid-spraying apparatus for purposes covered by this subclass
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A01N25/06—Aerosols
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to a one-component aqueous aerosol composition containing pyrethrum extract.
  • an aerosol stock solution containing (a) an insecticidal component, (b) a surfactant, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) water, and (e) Disclosed is a useful aerosol composition comprising a propellant and specifying a blending ratio of (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms and (d) water.
  • Most of the conventional aqueous aerosols for pest control, including these, are water-in-oil or oil-in-water emulsion preparations. For this reason, the liquid phase portion is separated in the aerosol container to form a two-component type, and it is necessary to shake the container to uniformly disperse the liquid phase portion before use.
  • aqueous aerosol As a one-component aqueous aerosol that improves on this point, for example, Prior Art 2 and Prior Art 3 are proposed. In both cases, dimethyl ether was used as the propellant, and the latter required an organic solvent such as a lower alcohol, and the performance evaluation as an aqueous aerosol was not satisfactory.
  • aqueous aerosol that has improved this point, for example, in the prior document 4, (a) an insecticidal component, (b) sorbitan fatty acid esters and polyoxyethylene polyoxypropylene alkyl ethers are blended to form a surface activity.
  • One-component aqueous aerosol consisting of an undiluted solution, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) an aerosol stock solution containing water, and (e) an LPG (liquefied petroleum gas) as a propellant.
  • (b) surfactant is 5 to 20% by volume based on the amount of aerosol stock solution, and (c) 40 to 78 aliphatic hydrocarbons having 8 to 16 carbon atoms are contained in the aerosol stock solution.
  • a blending ratio of sorbitan fatty acid esters and polyoxyethylene polyoxypropylene alkyl ethers is 1: 1 to 5 in (b) a surfactant containing 15 to 53% by volume of water and (d) water. 1:1 aqueous aerosol composition is disclosed.
  • pyrethrum extract obtained from pyrethrum, which is a plant of the Asteraceae family
  • pyrethrum extract contains natural pyrethrins which are a mixture of 6 kinds of compounds, and further contains plant-derived impurities. Therefore, it is required to add a surfactant more suitable for formulation of one-component aqueous aerosol. Was there.
  • JP 2001-89303 A Japanese Patent Publication No. 61-45601 Japanese Patent Publication No. 7-121848 JP, 2003-40704, A
  • the present invention provides a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. Is to provide.
  • the present inventors have conducted extensive studies, as a result, a composition in which a pyrethrum extract, a specific surfactant, an aerosol stock solution containing an aliphatic hydrocarbon and water, and a specific amount of a propellant are combined.
  • the present invention has been completed based on the knowledge that the object can be achieved by preparing a product.
  • the invention of claim 1 comprises (a) an insecticide chrysanthemum extract, (b) a surfactant, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) an aerosol stock solution containing water.
  • the (b) surfactant contains (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters, and the blending weight ratio [(f) / (g)] thereof is 0.5 ⁇ [(f).
  • the blending amount of the (d) water with respect to the total amount of the aerosol stock solution is 15 to 53% by mass (w/v)
  • the blending amount of the propellant (e) with respect to the total amount of the one-component aqueous aerosol composition is 40 to 70% by volume (v / v), which relates to the one-component aqueous aerosol composition.
  • the pyrethrum extract used in the present invention contains 6 kinds of natural pyrethrins, pyrethrin I, II, cinerin I, II, jasmorin I, II, plant-derived impurities, and a solvent. It is appropriate to use pyrethrum extract having a concentration of natural pyrethrins of 10% to 80%, and more preferably to use pyrethrum extract having a concentration of natural pyrethrins of 20 to 60%.
  • the appropriate amount of pyrethrum extract to be blended is about 0.01 to 5.0% by mass (w / v) as the content of natural pyrethrins in the aerosol stock solution, and less than 0.01% by mass (w / v).
  • the present invention uses a surfactant obtained by blending (b) polyethylene glycol alkyl esters and sorbitan fatty acid esters, and further, blending weight of (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters.
  • the ratio [(f)/(g)] is characterized in that 0.5 ⁇ [(f)/(g)] ⁇ 2.5.
  • polyethylene glycol alkyl esters include polyethylene glycol laurate, polyethylene glycol oleate, polyethylene glycol stearate, polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.
  • examples of the sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, and sorbitan monostearate.
  • the insecticide chrysanthemum extract It is not preferable because the solubility in the one-component aqueous aerosol composition is lowered, and the emulsion is not formed when the aerosol is formed, or even if it is formed, the stability of the emulsion is deteriorated. From the viewpoint of solubility in the one-component aqueous aerosol composition of pyrethrum extract and stability of the emulsion, 1.0 ⁇ [(f) / (g)] ⁇ 2.0 is more preferable.
  • polyoxyethylene polyoxypropylene alkyl ethers it is preferable to further add polyoxyethylene polyoxypropylene alkyl ethers to the above-mentioned surfactant from the viewpoint of solubility in the one-component aqueous aerosol composition of pyrethrum extract and stability of the emulsion.
  • polyoxyethylene polyoxypropylene alkyl ethers include polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene stearyl ether, and polyoxyethylene polyoxypropylene decyl tetradecyl ether.
  • the present invention is not limited to these.
  • surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers, as long as they do not interfere with the solubility of the insecticide chrysanthemum extract in a one-component aqueous aerosol composition and the stability of the emulsion.
  • Polyoxyethylene styrenated phenol, fatty acid ester of polyoxyethylene hydrogenated castor oil, diglyceryl alkyl ester and the like may be added.
  • the surfactant is blended in the aerosol stock solution of the present invention in a total amount of 5 to 20% by mass (w / v).
  • the amount of the aliphatic hydrocarbon having 8 to 16 carbon atoms to be blended with respect to the total amount of the aerosol stock solution is 40 to 78% by volume (v / v).
  • the insecticidal effect is low due to poor skin permeability to harmful insects, while when it exceeds 78% by volume (v/v), the problem of flammability cannot be solved, which is not preferable.
  • the aliphatic hydrocarbon include n-paraffin and isoparaffin, and n-paraffin is preferable in terms of efficacy.
  • Other types of organic solvents may be used as long as the characteristics of the present invention are not impaired.
  • the blending amount of (d) water in the aerosol stock solution is set to 15 to 53% by mass (w / v) in order to obtain a desired action / effect. If it is less than 15% by mass (w / v), the problem of flammability in the aerosol stock solution is not solved, while if it exceeds 53% by mass (w / v), it is difficult to improve the insecticidal efficacy.
  • E LPG (liquefied petroleum gas) is used as the propellant, but DME (dimethyl ether), freon gas, hydrofluoroolefin, compressed gas (nitrogen gas, carbon dioxide gas, etc.) is used within a range in which an emulsion can be produced. ) Etc. can be mixed.
  • the blending amount of the propellant is preferably limited to the range of 40 to 70% by volume (v / v) with respect to the total amount of the one-component aqueous aerosol composition.
  • the spray particles become coarse and a problem in insecticidal efficacy occurs, while if it exceeds 70% by volume (v / v), it is not preferable in terms of safety against fire.
  • the jet pressure may decrease.
  • LPG liquefied petroleum gas
  • propane ratio in propane / butane is increased. It is useful to use.
  • insecticidal components or repellent components to the one-component aqueous aerosol composition of the present invention as long as the solubility of the pyrethrum extract and the stability of the emulsion are not affected.
  • insecticidal components phenothrin, permethrin, ciphenothrin, cypermethrin, resmethrin, phthalthrin, allethrin, prarethrin, flamethrin, imiprothrin, etofenprox, bifenthrin, empentrin, metoflutrin, transfluthrin, profluthrin, monfluorothrin, etc.
  • Examples thereof include system insecticidal components, silicon-based insecticidal components such as silafluofen, neonicotinoid-based insecticidal components such as dinotefuran and acetamiprid, and organic phosphorus-based insecticidal components such as dichlorvos, phenothrin, and diazinone.
  • silicon-based insecticidal components such as silafluofen
  • neonicotinoid-based insecticidal components such as dinotefuran and acetamiprid
  • organic phosphorus-based insecticidal components such as dichlorvos, phenothrin, and diazinone.
  • repellent components N, N-diethyl-m-toramide, limonene, linalool, citronellal, menthol, menthol acetate, menthon, hinokithiol, geraniol, terpineol, p-menthan-3,8-diol, eucalyptus, curan- 3,4-diol, icaridine ⁇ 2- (2-hydroxyethyl) piperidine-1-carboxylic acid 1-methylpropyl ⁇ , IR-3535 ⁇ 3- [acetyl (butyl) amino] ethyl propionate ⁇ , peppermint oil, lemon Oil, lavender oil, eucalyptus oil and the like can be mentioned.
  • the one-component aqueous aerosol composition of the present invention includes an acaricide, a fungicide for fungi and bacteria, an antibacterial agent, a fungicide, a fragrance, and a deodorant.
  • a stabilizer, an antistatic agent, an antifoaming agent, an excipient and the like can be appropriately added.
  • the acaricide include 5-chloro-2-trifluoromethanesulfonamide methyl benzoate, phenyl salicylate, benzyl benzoate, dibutyl sebacate, 3-iodo-2-propynylbutylcarbamate and the like.
  • Antifungal agents, antibacterial agents, and bactericidal agents include hinokithiol, 2-mercaptobenzothiazole, 2- (4-thiazolin) benzimidazole, 5-chloro-2-methyl-4-isothiazolin-3-one, triphorin, 3 -Methyl-4-isopropylphenol, ortho-phenylphenol and the like can be mentioned.
  • aromatic agents examples include orange oil, lemon oil, lavender oil, peppermint oil, eucalyptus oil, citronella oil, lime oil, yuzu oil, jasmine oil, cypress oil, green tea essential oil, limonene, ⁇ -pinene, linalool, geraniol, phenylethyl.
  • aromatic components such as alcohol, amylcinnamic aldehyde, cumin aldehyde, and benzyl acetate, and fragrance components containing green leaf alcohol and green leaf aldehyde called "green scent".
  • Ebenaceae Gramineae, Theaceae (tea, etc.), Ginkgoaceae, Oleaceae (Malpighiaceae, etc.), Moraceae (Rutaceae, etc.), Rutaceae, Examples include one or more natural plant-derived substances selected from the family Quintlanaceae (such as acerola).
  • the blending weight ratio [(h)/(b)] of (a) the natural pyrethrins contained in the pyrethrum extract and the (b) surfactant is 0.005 ⁇ [(h)/(b). ] ⁇ 0.34 is appropriate, and if [(h) / (b)] ⁇ 0.005, the desired insecticidal effect cannot be obtained, and 0.34 ⁇ [(h) / (b)].
  • the surfactant in the configuration of the first aspect, (b) the surfactant further contains polyoxyethylene polyoxypropylene alkyl ethers.
  • the present invention provides a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. provide.
  • the aerosol stock solution is non-flammable, and a propellant is further blended to form a one-component aqueous aerosol composition.
  • a propellant is further blended to form a one-component aqueous aerosol composition.
  • the solubility of the pyrethrum extract in a one-component aqueous aerosol composition is excellent.
  • a one-component aqueous aerosol composition having excellent stability and exhibiting an excellent insecticidal effect against various pests is provided.
  • the aerosol stock solution is first put into a pressure-resistant container loaded with a valve portion, and then the propellant is pressurized and filled.
  • the shape of the valve, nozzle, nozzle, etc. can be appropriately selected for the aerosol agent according to its use, purpose of use, target pest, and the like, and various embodiments are possible.
  • pests to which the one-component aqueous aerosol composition of the present invention is effective include mosquitoes such as red-spotted mosquitoes and nettai shimaka, flies such as houseflies and houseflies, and dipteran pests such as cockroaches, bushes and abs. Pests such as cockroaches, ants, flies, mukades, and white ants, as well as indoor dust mites such as kona mites and chili mites, etc. are listed, and their practicality is extremely high.
  • the one-pack type aqueous aerosol composition of the present invention will be described in more detail based on specific examples and test examples.
  • the present invention is not limited to the examples below.
  • Example 1 Insect chrysanthemum extract (concentration of natural pyrethrins: 50%) 1.80 g (Insect chrysanthemum extract in aerosol stock solution is 1.80 mass% (w / v), natural pyrethrins is 0.90 mass% (w / v)) , Solbitan monolaurate 4.8 g (4.8% by mass (w / v) in aerosol stock solution), 5.6 g of polyethylene glycol monooleate (5.6% by mass (w / v) in aerosol stock solution), poly Oxyethylene polyoxypropylene decyl tetradecyl ether 2.4 g (2.4% by mass (w / v) in aerosol stock solution) and n-paraffin-based aliphatic saturated hydrocarbon having 11 to 14 carbon atoms (trade name: deotomisol) ) And 18 g of water (18 mass% (w / v) in the aerosol stock solution), 100 mL of the aero
  • the aerosol stock solution used in the present invention did not have a flash point measured based on the test method of the Fire Service Act, and it was considered that the problem of flammability was greatly reduced.
  • the one-component aqueous aerosol composition of the present invention is excellent in usability because it is a one-component type and it is not necessary to shake the container when using it.
  • an aerosol containing water is said to exhibit a lower insecticidal effect than an oil-based aerosol containing no water, but the efficacy of the aerosol containing the one-component aqueous aerosol composition of the present invention is It was almost comparable to the oil-based aerosol containing the same amount of pyrethrum extract.
  • Test Example 1 Various one-pack type aqueous aerosol compositions shown in Table 1 were prepared according to Example 1, and the following tests were conducted.
  • Solubility of pyrethrum extract The solubility of pyrethrum extract in various one-component aqueous aerosol compositions was visually confirmed. The results are shown by ⁇ , ⁇ , and x. ( ⁇ : 1 liquid, transparent, ⁇ : 1 liquid, translucent, ⁇ : not 1 liquid)
  • Emulsion stability Various one-component aqueous aerosol compositions were put in a pressure-resistant glass bottle and stored at 5°C and 45°C to examine the stability of the emulsion. The results are shown by ⁇ , ⁇ , and x. ( ⁇ : 1 liquid, transparent, ⁇ : 1 liquid, translucent, ⁇ : not 1 liquid)
  • Test example 2 The one-pack type aqueous aerosol compositions of Examples 1 and 2 and Comparative Example 5 in Table 1 were prepared to obtain aqueous aerosol agents.
  • n-paraffin-based aliphatic saturated hydrocarbon having 11 to 14 carbon atoms
  • the aerosol stock solution is placed in an aerosol container, a valve portion is attached to the container, and 150 mL of LPG (liquefied petroleum gas) (60% by volume (v / v) based on the total amount of the aerosol composition) is added through the valve portion.
  • LPG liquefied petroleum gas
  • the oil-based aerosol agent was prepared by pressure filling.
  • An oily aerosol agent was prepared in the same manner for Example 2 and Comparative Example 5. The following tests were conducted using various aerosol agents.
  • (1) Insecticidal efficacy test After releasing houseflies (about 25 adult males and females in one group) into a 60 cm cubic (0.216 m 3 ) glass chamber, the test aerosol was sprayed for 1 second, and the number of worms over time was recorded. ..
  • the KT50 value was determined, and the relative efficacy of the aqueous aerosol formulations (Examples 1 and 2 and Comparative Example 5) is shown in Table 2 with the efficacy of the oily aerosol formulation being 1.0.
  • the relative insecticidal efficacy was calculated by the formula of (KT50 value of oily aerosol)/(KT50 value of aqueous aerosol).
  • the one-component aqueous aerosol composition of the present invention was excellent in the solubility of pyrethrum extract.
  • it was a one-component type and had excellent emulsion stability, and its insecticidal efficacy was comparable to that of the control oil-based aerosol agent.
  • the blending weight ratio [(h)/(b)] of (h) natural pyrethrins contained in the pyrethrum extract and the above-mentioned (b) surfactant is 0.005 ⁇ [(h)/(b )] Examples 1 to 7, 9, 10 and 11 of ⁇ 0.25 were particularly excellent in the solubility and insecticidal efficacy of pyrethrum extract in the aerosol composition.
  • the surfactant is not a combination of (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters, and as in Comparative Example 3 and Comparative Example 7.
  • the compounding weight ratio [(f) / (g)] is out of the range of 0.5 ⁇ [(f) / (g)] ⁇ 2.5.
  • the solubility of the pyrethrum extract in the one-component aqueous aerosol composition was low, and the emulsion stability was poor. Further, when DME was used as the propellant (Comparative Example 4), the stability of the emulsion was lowered.
  • the present invention is a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. And is preferably used as an aqueous aerosol containing pyrethrum extract.

Abstract

Provided is a one-liquid-type aqueous aerosol composition having excellent solubility in an aerosol composition of a pyrethrum extract, and having excellent stability and insecticidal efficacy as a one-liquid-type aqueous aerosol composition.　This one-liquid-type aqueous aerosol composition contains: an undiluted aerosol solution containing (a) a pyrethrum extract, (b) a surfactant, (c) a C8-C16 aliphatic hydrocarbon, and (d) water; and (e) liquid petroleum gas (LPG) serving as a propellant. The (b) surfactant contains (f) a polyethylene glycol alkyl ester and (g) a sorbitan fatty acid ester, the blended weight ratio thereof [(f)/(g)] being 0.5 ≤ [(f)/(g)] ≤ 2.5, the blended amount of the (d) water relative to the total amount of the undiluted aerosol solution being 15-53 mass% (w/v), and the blended amount of the (e) propellant relative to the total amount of the one-liquid-type aqueous aerosol composition being 40-70 vol% (v/v).

Description

一液型水性エアゾール組成物One-part aqueous aerosol composition
　本発明は、除虫菊エキスを含有する一液型水性エアゾール組成物に関するものである。 The present invention relates to a one-component aqueous aerosol composition containing pyrethrum extract.
　従来より、製剤の引火性の問題を解決し、また環境問題の配慮、さらに使用感の向上を目的に水を配合した散布用水性殺虫剤や水性エアゾールに関して多数の提案がなされている。しかしながら、一般にその製剤化にあたっては、殺虫成分の疎水性を考慮し、均一な乳化安定性を得るためにアルコール等の水性有機溶剤を使用することが多かった。そして、これらの製剤は、水を含まない油性エアゾールに比べ、対象害虫の種類によっては殺虫効力面で劣る傾向があった。その理由は殺虫成分の害虫皮膚表面からの浸透性によるものと考えられる。 Many proposals have been made for water-based spraying insecticides and water-based aerosols containing water for the purpose of solving the problem of flammability of the preparation, consideration of environmental problems, and further improving the usability. However, in general, in the formulation thereof, in consideration of the hydrophobicity of the insecticidal component, an aqueous organic solvent such as alcohol is often used in order to obtain uniform emulsification stability. And, these formulations tended to be inferior in terms of insecticidal efficacy depending on the type of target pest, as compared with oil-based aerosols containing no water. It is considered that the reason is that the insecticidal component penetrates from the surface of the pest skin.
　先行文献１においては、（ａ）殺虫成分、（ｂ）界面活性剤、（ｃ）炭素数が８～１６個の脂肪族炭化水素、及び（ｄ）水を含有するエアゾール原液と、（ｅ）噴射剤とからなり、（ｃ）炭素数が８～１６個の脂肪族炭化水素、及び（ｄ）水の配合比を特定した有用なエアゾール組成物を開示している。これらを含め、従来の害虫防除用水性エアゾールの大部分は、油中水滴型もしくは水中油滴型のエマルジョン製剤である。このため、エアゾール容器内で液相部分が分離して二液型となっており、使用する前に容器を振とうして液相部分を均一に分散させる必要があった。 In Prior Art 1, an aerosol stock solution containing (a) an insecticidal component, (b) a surfactant, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) water, and (e) Disclosed is a useful aerosol composition comprising a propellant and specifying a blending ratio of (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms and (d) water. Most of the conventional aqueous aerosols for pest control, including these, are water-in-oil or oil-in-water emulsion preparations. For this reason, the liquid phase portion is separated in the aerosol container to form a two-component type, and it is necessary to shake the container to uniformly disperse the liquid phase portion before use.
　この点を改良した一液型の水性エアゾールとして、例えば先行文献２や先行文献３が提案されている。いずれも、噴射剤としてジメチルエーテルを使用し、後者においては更に低級アルコールなどの有機溶剤が必要とされ、水性エアゾールとしての性能評価は満足のいくものではなかった。 As a one-component aqueous aerosol that improves on this point, for example, Prior Art 2 and Prior Art 3 are proposed. In both cases, dimethyl ether was used as the propellant, and the latter required an organic solvent such as a lower alcohol, and the performance evaluation as an aqueous aerosol was not satisfactory.
　この点を改良した一液型の水性エアゾールとして、例えば先行文献４においては、（ａ）殺虫成分、（ｂ）ソルビタン脂肪酸エステル類及びポリオキシエチレンポリオキシプロピレンアルキルエーテル類を配合してなる界面活性剤、（ｃ）炭素数が８～１６個の脂肪族炭化水素、及び（ｄ） 水を含有するエアゾール原液と、（ｅ） 噴射剤としてのＬＰＧ（液化石油ガス）からなる一液型水性エアゾール組成物であって、該エアゾール原液中に、（ｂ）界面活性剤がエアゾール原液量に対して５～２０容量％、（ｃ） 炭素数が８～１６個の脂肪族炭化水素が４０～７８容量％、及び（ｄ）水が１５～５３容量％含有され、かつ、（ｂ）界面活性剤において、ソルビタン脂肪酸エステル類とポリオキシエチレンポリオキシプロピレンアルキルエーテル類の配合比が１：１～５：１であることを特徴とする一液型水性エアゾール組成物を開示している。 As a one-component aqueous aerosol that has improved this point, for example, in the prior document 4, (a) an insecticidal component, (b) sorbitan fatty acid esters and polyoxyethylene polyoxypropylene alkyl ethers are blended to form a surface activity. One-component aqueous aerosol consisting of an undiluted solution, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) an aerosol stock solution containing water, and (e) an LPG (liquefied petroleum gas) as a propellant. In the composition, (b) surfactant is 5 to 20% by volume based on the amount of aerosol stock solution, and (c) 40 to 78 aliphatic hydrocarbons having 8 to 16 carbon atoms are contained in the aerosol stock solution. A blending ratio of sorbitan fatty acid esters and polyoxyethylene polyoxypropylene alkyl ethers is 1: 1 to 5 in (b) a surfactant containing 15 to 53% by volume of water and (d) water. 1:1 aqueous aerosol composition is disclosed.
　ところで近年、消費者による天然志向が高まり、天然成分を有効成分として含有する殺虫剤に対するニーズが高まっている。水性エアゾールにおいても有効成分にキク科植物である除虫菊から得られる除虫菊エキス等の天然成分を含有する製品が求められている。一般に、除虫菊エキスは６種類の化合物の混合物である天然ピレトリン類を含有し、さらに植物由来の不純物を含むため、一液型水性エアゾールの製剤化により適した界面活性剤を配合することが求められていた。 By the way, in recent years, consumers are becoming more and more natural, and there is a growing need for insecticides containing natural ingredients as active ingredients. Even in aqueous aerosols, products containing natural ingredients such as pyrethrum extract obtained from pyrethrum, which is a plant of the Asteraceae family, are required as active ingredients. In general, pyrethrum extract contains natural pyrethrins which are a mixture of 6 kinds of compounds, and further contains plant-derived impurities. Therefore, it is required to add a surfactant more suitable for formulation of one-component aqueous aerosol. Was there.
特開２００１－８９３０３号公報JP 2001-89303 A 特公昭６１－４５６０１号公報Japanese Patent Publication No. 61-45601 特公平７－１２１８４８号公報Japanese Patent Publication No. 7-121848 特開２００３－４０７０４号公報JP, 2003-40704, A
　本発明は、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性に優れ、一液型水性エアゾール組成物の安定性にも優れ、さらに殺虫効力面にも優れた一液型水性エアゾール組成物を提供することである。 The present invention provides a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. Is to provide.
　上記課題を解決するため、本発明者らは鋭意研究を重ねた結果、除虫菊エキスと特定の界面活性剤と脂肪族炭化水素及び水を含有するエアゾール原液、更に噴射剤の特定量を組み合わせた組成物を調製することによって目的を達成できることの知見を得て、本発明を完成した。 In order to solve the above problems, the present inventors have conducted extensive studies, as a result, a composition in which a pyrethrum extract, a specific surfactant, an aerosol stock solution containing an aliphatic hydrocarbon and water, and a specific amount of a propellant are combined. The present invention has been completed based on the knowledge that the object can be achieved by preparing a product.
　すなわち請求項１の発明は、（ａ）除虫菊エキス、（ｂ）界面活性剤、（ｃ）炭素数が８～１６個の脂肪族炭化水素、及び（ｄ）水を含有するエアゾール原液と、（ｅ）噴射剤としてのＬＰＧ（液化石油ガス）とを含有する一液型水性エアゾール組成物であって、
　前記（ｂ）界面活性剤は、（ｆ）ポリエチレングリコールアルキルエステル類と（ｇ）ソルビタン脂肪酸エステル類を含有し、その配合重量比［（ｆ）／（ｇ）］は０．５≦［（ｆ）／（ｇ）］≦２．５であり、
　前記（ｄ）水の当該エアゾール原液全体量に対する配合量は１５～５３質量％（ｗ／ｖ）であり、
　かつ、前記（ｅ）噴射剤の当該一液型水性エアゾール組成物全体量に対する配合量は４０～７０容量％（ｖ／ｖ）である一液型水性エアゾール組成物に係るものである。 That is, the invention of claim 1 comprises (a) an insecticide chrysanthemum extract, (b) a surfactant, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) an aerosol stock solution containing water. e) A one-pack type aqueous aerosol composition containing LPG (liquefied petroleum gas) as a propellant,
The (b) surfactant contains (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters, and the blending weight ratio [(f) / (g)] thereof is 0.5 ≦ [(f). )/(G)]≦2.5,
The blending amount of the (d) water with respect to the total amount of the aerosol stock solution is 15 to 53% by mass (w/v),
Moreover, the blending amount of the propellant (e) with respect to the total amount of the one-component aqueous aerosol composition is 40 to 70% by volume (v / v), which relates to the one-component aqueous aerosol composition.
　本発明で用いる除虫菊エキスはピレトリンＩ、ＩＩ、シネリンＩ、ＩＩ、ジャスモリンＩ、ＩＩの６種類の天然ピレトリン類 、植物由来の不純物、及び溶剤を含んでいる。天然ピレトリン類の濃度が１０％～８０％の除虫菊エキスを用いるのが適当であり、天然ピレトリン類の濃度が２０～６０％の除虫菊エキスを用いるのがより好ましい。除虫菊エキスの配合量は、エアゾール原液中の天然ピレトリン類の含有量として０．０１～５．０質量 ％（ｗ／ｖ）程度が適当であり、０．０１質量％（ｗ／ｖ）未満であると所望の殺虫効果が得られない。一方、５．０質量％（ｗ／ｖ）を超えると除虫菊エキスの一液型水性エアゾール組成物に対する溶解性に問題を生じる場合がある。除虫菊エキスの一液型水性エアゾール組成物に対する溶解性や殺虫効力の観点から０．２０～３．０質量 ％（ｗ／ｖ）程度がより好ましい。なお、除虫菊エキスの産地や各成分の組成比は限定されない。 The pyrethrum extract used in the present invention contains 6 kinds of natural pyrethrins, pyrethrin I, II, cinerin I, II, jasmorin I, II, plant-derived impurities, and a solvent. It is appropriate to use pyrethrum extract having a concentration of natural pyrethrins of 10% to 80%, and more preferably to use pyrethrum extract having a concentration of natural pyrethrins of 20 to 60%. The appropriate amount of pyrethrum extract to be blended is about 0.01 to 5.0% by mass (w / v) as the content of natural pyrethrins in the aerosol stock solution, and less than 0.01% by mass (w / v). If so, the desired insecticidal effect cannot be obtained. On the other hand, if it exceeds 5.0% by mass (w / v), there may be a problem in the solubility of pyrethrum extract in a one-component aqueous aerosol composition. From the viewpoint of solubility in the one-component aqueous aerosol composition of pyrethrum extract and insecticidal efficacy, about 0.20 to 3.0% by mass (w / v) is more preferable. The origin of the pyrethrum extract and the composition ratio of each component are not limited.
　本発明は、（ｂ）ポリエチレングリコールアルキルエステル類及びソルビタン脂肪酸エステル類を配合してなる界面活性剤を使用し、更に、（ｆ）ポリエチレングリコールアルキルエステル類と（ｇ）ソルビタン脂肪酸エステル類の配合重量比［（ｆ）／（ｇ）］を０．５≦［（ｆ）／（ｇ）］≦２．５としたことに特徴を有する。ポリエチレングリコールアルキルエステル類としては、ポリエチレングリコールラウレート、ポリエチレングリコールオレエート、ポリエチレングリコールステアレート、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノオレエート、ポリエチレングリコールモノステアレートなどが例示できる。一方、ソルビタン脂肪酸エステル類としては、ソルビタンモノラウレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ソルビタントリオレエート、ソルビタンモノステアレートなどが挙げられる。ポリエチレングリコールアルキルエステル類とソルビタン脂肪酸エステル類の配合重量比［（ｆ）／（ｇ）］が０．５≦［（ｆ）／（ｇ）］≦２．５の範囲を外れると、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性が低下し、また、エアゾールにした時にエマルジョンが形成されないか、もしくは形成されてもエマルジョンの安定性が悪くなり、好ましくない。除虫菊エキスの一液型水性エアゾール組成物に対する溶解性やエマルジョンの安定性の観点から１．０≦［（ｆ）／（ｇ）］≦２．０がより好ましい。 The present invention uses a surfactant obtained by blending (b) polyethylene glycol alkyl esters and sorbitan fatty acid esters, and further, blending weight of (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters. The ratio [(f)/(g)] is characterized in that 0.5≦[(f)/(g)]≦2.5. Examples of polyethylene glycol alkyl esters include polyethylene glycol laurate, polyethylene glycol oleate, polyethylene glycol stearate, polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate. On the other hand, examples of the sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, and sorbitan monostearate. When the compounding weight ratio [(f) / (g)] of polyethylene glycol alkyl esters and sorbitan fatty acid esters is out of the range of 0.5 ≦ [(f) / (g)] ≦ 2.5, the insecticide chrysanthemum extract It is not preferable because the solubility in the one-component aqueous aerosol composition is lowered, and the emulsion is not formed when the aerosol is formed, or even if it is formed, the stability of the emulsion is deteriorated. From the viewpoint of solubility in the one-component aqueous aerosol composition of pyrethrum extract and stability of the emulsion, 1.0 ≦ [(f) / (g)] ≦ 2.0 is more preferable.
　本発明では、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性やエマルジョンの安定性の点から、上記配合の界面活性剤中に更にポリオキシエチレンポリオキシプロピレンアルキルエーテル類を配合するのが好ましい。ポリオキシエチレンポリオキシプロピレンアルキルエーテル類としては、ポリオキシエチレンポリオキシプロピレンセチルエーテル、ポリオキシエチレンポリオキシプロピレンラウリルエーテル、ポリオキシエチレンポリオキシプロピレンステアリルエーテル、ポリオキシエチレンポリオキシプロピレンデシルテトラデシルエーテルなどがあげられるがこれらに限定されない。また、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性やエマルジョンの安定性に支障をきたさない限りにおいて、他のタイプの界面活性剤、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンスチレン化フェノール、ポリオキシエチレン硬化ヒマシ油の脂肪酸エステル、ジグリセリルアルキルエステルなどを加えてもよい。さらに、界面活性剤は、本発明エアゾール原液中にトータルとして５～２０質量％（ｗ／ｖ）配合されるのが適当である。５質量％（ｗ／ｖ）未満であると十分なエマルジョンが得られず、一方２０質量％（ｗ／ｖ）を超えるとべた付きなどの使用感に影響を及ぼし、水性エアゾールのメリットが得られないので好ましくない。 In the present invention, it is preferable to further add polyoxyethylene polyoxypropylene alkyl ethers to the above-mentioned surfactant from the viewpoint of solubility in the one-component aqueous aerosol composition of pyrethrum extract and stability of the emulsion. .. Examples of polyoxyethylene polyoxypropylene alkyl ethers include polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene stearyl ether, and polyoxyethylene polyoxypropylene decyl tetradecyl ether. However, the present invention is not limited to these. In addition, other types of surfactants, such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers, as long as they do not interfere with the solubility of the insecticide chrysanthemum extract in a one-component aqueous aerosol composition and the stability of the emulsion. , Polyoxyethylene styrenated phenol, fatty acid ester of polyoxyethylene hydrogenated castor oil, diglyceryl alkyl ester and the like may be added. Further, it is appropriate that the surfactant is blended in the aerosol stock solution of the present invention in a total amount of 5 to 20% by mass (w / v). If it is less than 5% by mass (w / v), a sufficient emulsion cannot be obtained, while if it exceeds 20% by mass (w / v), it affects the usability such as stickiness, and the merit of an aqueous aerosol can be obtained. It's not preferable because it doesn't exist.
　本発明では、（ｃ）炭素数が８～１６個の脂肪族炭化水素の、エアゾール原液全体量に対する配合量は４０～７８容量％（ｖ／ｖ）である。４０容量％（ｖ／ｖ）未満であると害虫に対する皮膚浸透性が悪いため殺虫効力が低く、一方、７８容量％（ｖ／ｖ）を超えると引火性の問題が解消されないので好ましくない。脂肪族炭化水素としては、ｎ－パラフィン又はイソパラフィンがあげられるが、効力の点においてｎ－パラフィンが好ましい。なお、本発明の特性を損なわない範囲において、他の種類の有機溶剤を使用してもよい。 In the present invention, (c) the amount of the aliphatic hydrocarbon having 8 to 16 carbon atoms to be blended with respect to the total amount of the aerosol stock solution is 40 to 78% by volume (v / v). When it is less than 40% by volume (v/v), the insecticidal effect is low due to poor skin permeability to harmful insects, while when it exceeds 78% by volume (v/v), the problem of flammability cannot be solved, which is not preferable. Examples of the aliphatic hydrocarbon include n-paraffin and isoparaffin, and n-paraffin is preferable in terms of efficacy. Other types of organic solvents may be used as long as the characteristics of the present invention are not impaired.
　また本発明では、所望の作用・効果を得るために、エアゾール原液中の（ｄ）水の配合量は１５～５３質量％（ｗ／ｖ）に設定される。１５質量％（ｗ／ｖ）未満であるとエアゾール原液における引火性の問題が解消されず、一方、５３質量％（ｗ／ｖ）を超えると殺虫効力の改善が難しい。 Further, in the present invention, the blending amount of (d) water in the aerosol stock solution is set to 15 to 53% by mass (w / v) in order to obtain a desired action / effect. If it is less than 15% by mass (w / v), the problem of flammability in the aerosol stock solution is not solved, while if it exceeds 53% by mass (w / v), it is difficult to improve the insecticidal efficacy.
　（ｅ）噴射剤としては、ＬＰＧ（液化石油ガス）が使用されるが、エマルジョンの生成が可能な範囲内で、ＤＭＥ（ジメチルエーテル）、フロンガス、ハイドロフルオロオレフィン、圧縮ガス（窒素ガス、炭酸ガス等）などを混合することは差支えない。また、噴射剤の配合量としては、一液型水性エアゾール組成物全体量に対して４０～７０容量％（ｖ／ｖ）の範囲に抑えるのが好ましい。４０容量％（ｖ／ｖ）未満では、噴霧粒子が粗くなって殺虫効力に問題が生じるし、一方、７０容量％（ｖ／ｖ）を超えると火気に対する安全性の点で好ましくない。なお、噴射剤の配合量を減らしたり、圧縮ガスを使用した場合、噴射圧の低下を招くことがあるので、その対策として例えば、プロパン／ブタン中のプロパン比率を高めたＬＰＧ（液化石油ガス）を使用することは有用である。 (E) LPG (liquefied petroleum gas) is used as the propellant, but DME (dimethyl ether), freon gas, hydrofluoroolefin, compressed gas (nitrogen gas, carbon dioxide gas, etc.) is used within a range in which an emulsion can be produced. ) Etc. can be mixed. The blending amount of the propellant is preferably limited to the range of 40 to 70% by volume (v / v) with respect to the total amount of the one-component aqueous aerosol composition. If it is less than 40% by volume (v / v), the spray particles become coarse and a problem in insecticidal efficacy occurs, while if it exceeds 70% by volume (v / v), it is not preferable in terms of safety against fire. If the blending amount of the propellant is reduced or compressed gas is used, the jet pressure may decrease. As a countermeasure, for example, LPG (liquefied petroleum gas) in which the propane ratio in propane / butane is increased. It is useful to use.
　また、本発明の一液型水性エアゾール組成物には、除虫菊エキスの溶解性やエマルジョンの安定性に影響を及ぼさない範囲で他の殺虫成分や忌避成分を配合することも可能である。例えば、殺虫成分としてフェノトリン、ぺルメトリン、シフェノトリン、シペルメトリン、レスメトリン、フタルスリン、アレスリン、プラレトリン、フラメトリン、イミプロトリン、エトフェンプロックス、ビフェントリン、エンペントリン、メトフルトリン、トランスフルトリン、プロフルトリン、モンフルオロトリン等のピレスロイド系殺虫成分、シラフルオフェン等のケイ素系殺虫成分、ジノテフラン、アセタミプリド等のネオニコチノイド系殺虫成分、ジクロルボス、フェニトロチオン、ダイアジノン等の有機リン系殺虫成分があげられる。また、忌避成分としてＮ，Ｎ－ジエチル－ｍ－トルアミド、リモネン、リナロール、シトロネラール、メントール、酢酸メンチル、メントン、ヒノキチオール、ゲラニオール、テルピネオール、ｐ－メンタン－３，８－ジオール、ユーカリプトール、カラン－３，４－ジオール、イカリジン｛２－（２－ヒドロキシエチル）ピペリジン－１－カルボン酸１－メチルプロピル｝、ＩＲ－３５３５｛３－［アセチル（ブチル）アミノ］プロピオン酸エチル｝、ハッカ油、レモン油、ラベンダー油、ユーカリ油等が挙げられる。 Further, it is possible to add other insecticidal components or repellent components to the one-component aqueous aerosol composition of the present invention as long as the solubility of the pyrethrum extract and the stability of the emulsion are not affected. For example, as insecticidal components, phenothrin, permethrin, ciphenothrin, cypermethrin, resmethrin, phthalthrin, allethrin, prarethrin, flamethrin, imiprothrin, etofenprox, bifenthrin, empentrin, metoflutrin, transfluthrin, profluthrin, monfluorothrin, etc. Examples thereof include system insecticidal components, silicon-based insecticidal components such as silafluofen, neonicotinoid-based insecticidal components such as dinotefuran and acetamiprid, and organic phosphorus-based insecticidal components such as dichlorvos, phenothrin, and diazinone. In addition, as repellent components, N, N-diethyl-m-toramide, limonene, linalool, citronellal, menthol, menthol acetate, menthon, hinokithiol, geraniol, terpineol, p-menthan-3,8-diol, eucalyptus, curan- 3,4-diol, icaridine {2- (2-hydroxyethyl) piperidine-1-carboxylic acid 1-methylpropyl}, IR-3535 {3- [acetyl (butyl) amino] ethyl propionate}, peppermint oil, lemon Oil, lavender oil, eucalyptus oil and the like can be mentioned.
　また、本発明の一液型水性エアゾール組成物には、殺虫成分以外に殺ダニ剤、カビ類や細菌類等を対象とした防カビ剤、抗菌剤、殺菌剤、芳香剤、消臭剤、安定化剤、帯電防止剤、消泡剤、賦形剤等を適宜配合することもできる。殺ダニ剤としては、５－クロロ－２－トリフルオロメタンスルホンアミド安息香酸メチル、サリチル酸フェニル、安息香酸ベンジル、セバシン酸ジブチル、３－ヨード－２－プロピニルブチルカーバメート等が挙げられる。防カビ剤、抗菌剤、及び殺菌剤としては、ヒノキチオール、２－メルカプトベンゾチアゾール、２－（４－チアゾリル）ベンツイミダゾール、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、トリホリン、３－メチル－４－イソプロピルフェノール、オルト－フェニルフェノール等が挙げられる。芳香剤としては、オレンジ油、レモン油、ラベンダー油、ペパーミント油、ユーカリ油、シトロネラ油、ライム油、ユズ油、ジャスミン油、檜油、緑茶精油、リモネン、α－ピネン、リナロール、ゲラニオール、フェニルエチルアルコール、アミルシンナミックアルデヒド、クミンアルデヒド、ベンジルアセテート等の芳香成分、「緑の香り」と呼ばれる青葉アルコールや青葉アルデヒド配合の香料成分等が挙げられる。消臭剤としては、各種のものが使用可能であるが、カキノキ科、イネ科、ツバキ科（茶など）、イチョウ科、モクセイ科（シナレンギョウなど）、クワ科（イチジクなど）、ミカン科、キントラノオ科（アセロラなど）の中から選ばれる１種以上の天然の植物由来物質等が挙げられる。 In addition to the insecticidal component, the one-component aqueous aerosol composition of the present invention includes an acaricide, a fungicide for fungi and bacteria, an antibacterial agent, a fungicide, a fragrance, and a deodorant. A stabilizer, an antistatic agent, an antifoaming agent, an excipient and the like can be appropriately added. Examples of the acaricide include 5-chloro-2-trifluoromethanesulfonamide methyl benzoate, phenyl salicylate, benzyl benzoate, dibutyl sebacate, 3-iodo-2-propynylbutylcarbamate and the like. Antifungal agents, antibacterial agents, and bactericidal agents include hinokithiol, 2-mercaptobenzothiazole, 2- (4-thiazolin) benzimidazole, 5-chloro-2-methyl-4-isothiazolin-3-one, triphorin, 3 -Methyl-4-isopropylphenol, ortho-phenylphenol and the like can be mentioned. Examples of aromatic agents include orange oil, lemon oil, lavender oil, peppermint oil, eucalyptus oil, citronella oil, lime oil, yuzu oil, jasmine oil, cypress oil, green tea essential oil, limonene, α-pinene, linalool, geraniol, phenylethyl. Examples include aromatic components such as alcohol, amylcinnamic aldehyde, cumin aldehyde, and benzyl acetate, and fragrance components containing green leaf alcohol and green leaf aldehyde called "green scent". Various deodorants can be used, but Ebenaceae, Gramineae, Theaceae (tea, etc.), Ginkgoaceae, Oleaceae (Malpighiaceae, etc.), Moraceae (Rutaceae, etc.), Rutaceae, Examples include one or more natural plant-derived substances selected from the family Quintlanaceae (such as acerola).
　請求項２の発明は、請求項１の構成において、（ａ）除虫菊エキスに含まれる（ｈ）天然ピレトリン類と、前記（ｂ）界面活性剤との配合重量比［（ｈ）／（ｂ）］は、０．００５≦［（ｈ）／（ｂ）］≦０．３４としたものである。 According to the invention of claim 2, in the constitution of claim 1, a blending weight ratio [(h)/(b) of (a) the natural pyrethrins contained in the pyrethrum extract and the (b) surfactant. ] Is 0.005≦[(h)/(b)]≦0.34.
　（ａ）除虫菊エキスに含まれる（ｈ）天然ピレトリン類と、前記（ｂ）界面活性剤との配合重量比［（ｈ）／（ｂ）］は０．００５≦［（ｈ）／（ｂ）］≦０．３４が適当であり、［（ｈ）／（ｂ）］＜０．００５であると所望の殺虫効果が得られず、０．３４＜［（ｈ）／（ｂ）］であると除虫菊エキスの一液型水性エアゾール組成物に対する溶解性やエマルジョンの安定性に問題が生じる場合がある。中でも除虫菊エキスの一液型水性エアゾール組成物に対する溶解性や殺虫効力の観点から０．００５≦［（ｈ）／（ｂ）］≦０．２５がより好ましい。 The blending weight ratio [(h)/(b)] of (a) the natural pyrethrins contained in the pyrethrum extract and the (b) surfactant is 0.005≦[(h)/(b). ] ≤ 0.34 is appropriate, and if [(h) / (b)] <0.005, the desired insecticidal effect cannot be obtained, and 0.34 <[(h) / (b)]. There may be a problem in the solubility of the pyrethrum extract in the one-component aqueous aerosol composition and the stability of the emulsion. Of these, 0.005 ≦ [(h) / (b)] ≦ 0.25 is more preferable from the viewpoint of solubility and insecticidal efficacy of pyrethrum extract in a one-component aqueous aerosol composition.
　請求項３の発明は、請求項１の構成において、（ｂ）界面活性剤に、さらにポリオキシエチレンポリオキシプロピレンアルキルエーテル類を含有するものである。 According to the third aspect of the present invention, in the configuration of the first aspect, (b) the surfactant further contains polyoxyethylene polyoxypropylene alkyl ethers.
　ポリオキシエチレンポリオキシプロピレンアルキルエーテル類の配合により、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性やエマルジョンの安定性が向上する。 By blending polyoxyethylene polyoxypropylene alkyl ethers, the solubility of pyrethrum extract in a one-component aqueous aerosol composition and the stability of the emulsion are improved.
　本発明は、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性に優れ、一液型水性エアゾール組成物の安定性にも優れ、さらに殺虫効力面にも優れた一液型水性エアゾール組成物を提供する。 The present invention provides a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. provide.
　本発明の請求項１乃至３のいずれかの構成によると、エアゾール原液は非引火性であり、更に噴射剤を配合して一液型水性エアゾール組成物となしたので、使用の際に容器を振とうする必要がなく使用に優れる。また、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性に優れる。さらに一液型水性エアゾール組成物の安定性に優れ、種々の害虫に対して優れた殺虫効力を奏する極めて有用な一液型水性エアゾール組成物が提供される。エアゾール剤を製造するにあたっては、通常、バルブ部分を装填した耐圧容器にまずエアゾール原液を入れた後、噴射剤を加圧充填して製造する。エアゾール剤は、その用途、使用目的、対象害虫等に応じて、適宜バルブ、噴口、ノズル等の形状を選択することができ、種々の実施の形態が可能である。 According to any of the configurations of claims 1 to 3 of the present invention, the aerosol stock solution is non-flammable, and a propellant is further blended to form a one-component aqueous aerosol composition. Excellent to use without the need for shaking. Moreover, the solubility of the pyrethrum extract in a one-component aqueous aerosol composition is excellent. Further, a one-component aqueous aerosol composition having excellent stability and exhibiting an excellent insecticidal effect against various pests is provided. In the production of an aerosol agent, usually, the aerosol stock solution is first put into a pressure-resistant container loaded with a valve portion, and then the propellant is pressurized and filled. The shape of the valve, nozzle, nozzle, etc. can be appropriately selected for the aerosol agent according to its use, purpose of use, target pest, and the like, and various embodiments are possible.
　本発明の一液型水性エアゾール組成物が有効な害虫としては、例えば、アカイエカ、ネッタイシマカ等のカ類、ユスリカ類、イエバエ等のハエ類、チョウバエ、ブユ類、アブ類等の双翅目害虫やゴキブリ類、アリ類、ヤスデ、ムカデ類、シロアリ類等の匍匐害虫、さらにコナダニ、チリダニ等の屋内塵性ダニ類等があげられ、その実用性は極めて高いものである。 Examples of pests to which the one-component aqueous aerosol composition of the present invention is effective include mosquitoes such as red-spotted mosquitoes and nettai shimaka, flies such as houseflies and houseflies, and dipteran pests such as cockroaches, bushes and abs. Pests such as cockroaches, ants, flies, mukades, and white ants, as well as indoor dust mites such as kona mites and chili mites, etc. are listed, and their practicality is extremely high.
　つぎに具体的実施例ならびに試験例に基づいて、本発明の一液型水性エアゾール組成物を更に詳細に説明する。なお、本発明は以下の実施例に限定されるものではない。 Next, the one-pack type aqueous aerosol composition of the present invention will be described in more detail based on specific examples and test examples. The present invention is not limited to the examples below.
　実施例１．除虫菊エキス（天然ピレトリン類の濃度：５０％）１．８０ｇ（エアゾール原液中に除虫菊エキスは１．８０質量％（ｗ／ｖ）で、天然ピレトリン類は０．９０質量％（ｗ／ｖ））、ソルビタンモノラウレート４．８ｇ（エアゾール原液中、４．８質量％（ｗ／ｖ））、ポリエチレングリコールモノオレエート５．６ｇ（エアゾール原液中５．６質量％（ｗ／ｖ））、ポリオキシエチレンポリオキシプロピレンデシルテトラデシルエーテル２．４ｇ（エアゾール原液中２．４質量％（ｗ／ｖ））に炭素数が１１ ～１４個のｎ－パラフィン系脂肪族飽和炭化水素（商品名：デオトミゾール）及び水１８ｇ（エアゾール原液中１８質量％（ｗ／ｖ））からなるエアゾール原液１００ｍＬをエアゾール容器に入れ、該容器にバルブ部分を取付け、該バルブ部分を通じて、ＬＰＧ（液化石油ガス）１５０ｍＬ（一液型水性エアゾール組成物全体量に対して、６０容量％（ｖ／ｖ））を加圧充填して、本発明の一液型水性エアゾール組成物を含むエアゾール剤を得た。 Example 1. Insect chrysanthemum extract (concentration of natural pyrethrins: 50%) 1.80 g (Insect chrysanthemum extract in aerosol stock solution is 1.80 mass% (w / v), natural pyrethrins is 0.90 mass% (w / v)) , Solbitan monolaurate 4.8 g (4.8% by mass (w / v) in aerosol stock solution), 5.6 g of polyethylene glycol monooleate (5.6% by mass (w / v) in aerosol stock solution), poly Oxyethylene polyoxypropylene decyl tetradecyl ether 2.4 g (2.4% by mass (w / v) in aerosol stock solution) and n-paraffin-based aliphatic saturated hydrocarbon having 11 to 14 carbon atoms (trade name: deotomisol) ) And 18 g of water (18 mass% (w / v) in the aerosol stock solution), 100 mL of the aerosol stock solution is placed in an aerosol container, a valve part is attached to the container, and 150 mL of LPG (liquefied petroleum gas) is passed through the valve part. 60% by volume (v / v)) was pressurized and filled with respect to the total amount of the liquid aqueous aerosol composition to obtain an aerosol agent containing the one liquid aqueous aerosol composition of the present invention.
　本発明で用いたエアゾール原液は、消防法の試験方法に基づく引火点が測定されず、引火性の問題が非常に軽減されたものと考えられた。また、本発明の一液型水性エアゾール組成物は、一液型で使用の際に容器を振とうする必要がなく使用性に優れた。更に、水を配合したエアゾール剤は、水を含まない油性エアゾール剤に比べて低い殺虫効果を示すと言われているが、本発明の一液型水性エアゾール組成物を含むエアゾール剤の効力は、同量の除虫菊エキスを含む油性エアゾール剤とほとんど遜色ないものであった。 The aerosol stock solution used in the present invention did not have a flash point measured based on the test method of the Fire Service Act, and it was considered that the problem of flammability was greatly reduced. In addition, the one-component aqueous aerosol composition of the present invention is excellent in usability because it is a one-component type and it is not necessary to shake the container when using it. Furthermore, an aerosol containing water is said to exhibit a lower insecticidal effect than an oil-based aerosol containing no water, but the efficacy of the aerosol containing the one-component aqueous aerosol composition of the present invention is It was almost comparable to the oil-based aerosol containing the same amount of pyrethrum extract.
　試験例１．実施例１に準じて表１に示す各種一液型水性エアゾール組成物を調製し、下記に示す試験を行った。
（１）除虫菊エキスの溶解性；除虫菊エキスの各種一液型水性エアゾール組成物に対する溶解性を目視にて確認した。結果を、○、△、×で示した。
（○：一液、透明、△：一液、半透明、×：一液ではない）
（２）エマルジョンの安定性；各種一液型水性エアゾール組成物を耐圧ガラスびんに入れ、５℃と４５℃に保存してエマルジョンの安定性を調べた。結果を、○、△、×で示した。
（○：一液、透明、△：一液、半透明、×：一液ではない） Test Example 1. Various one-pack type aqueous aerosol compositions shown in Table 1 were prepared according to Example 1, and the following tests were conducted.
(1) Solubility of pyrethrum extract: The solubility of pyrethrum extract in various one-component aqueous aerosol compositions was visually confirmed. The results are shown by ◯, Δ, and x.
(○: 1 liquid, transparent, △: 1 liquid, translucent, ×: not 1 liquid)
(2) Emulsion stability: Various one-component aqueous aerosol compositions were put in a pressure-resistant glass bottle and stored at 5°C and 45°C to examine the stability of the emulsion. The results are shown by ◯, Δ, and x.
(○: 1 liquid, transparent, △: 1 liquid, translucent, ×: not 1 liquid)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　試験例２．表１の実施例１、２及び比較例５の一液型水性エアゾール組成物を調製して水性エアゾール剤を得た。また、実施例１と同量の除虫菊エキス（天然ピレトリン類の濃度：５０％）１．８０ｇ（エアゾール原液中に除虫菊エキスは１．８０質量％（ｗ／ｖ）で、天然ピレトリン類は０．９０質量％（ｗ／ｖ））を炭素数が１１～１４個のｎ－パラフィン系脂肪族飽和炭化水素（商品名：デオトミゾール）に溶解させ、エアゾール原液１００ｍＬとする。該エアゾール原液をエアゾール容器に入れ、該容器にバルブ部分を取付け、該バルブ部分を通じて、ＬＰＧ（液化石油ガス）１５０ｍＬ（エアゾール組成物全体量に対して、６０容量％（ｖ／ｖ））を加圧充填して、油性エアゾール剤を調整した。実施例２及び比較例５に関しても同様に油性エアゾール剤を調製した。各種エアゾール剤を用いて下記に示す試験を行った。
　（１）殺虫効力試験（ガラスチャンバー法）
６０ｃｍ立方（０．２１６ｍ3)のガラスチャンバーにイエバエ（１群約 ２５匹の雄雌成虫）を放った後、供試エアゾールを１秒間噴霧し、時間の経過に伴う仰転虫数を記録した。ＫＴ50値を求め、油性エアゾール剤の効力を１．０として水性エアゾール剤（実施例１、２及び比較例５）の相対効力を表２に示した。なお、相対殺虫効力は（油性エアゾール剤のＫＴ５０値）／（水性エアゾールのＫＴ５０値）の式により算出した。 Test example 2. The one-pack type aqueous aerosol compositions of Examples 1 and 2 and Comparative Example 5 in Table 1 were prepared to obtain aqueous aerosol agents. In addition, the same amount of pyrethrin extract (concentration of natural pyrethrins: 50%) as in Example 1 was 1.80 g (the pyrethrin extract was 1.80% by mass (w / v) in the aerosol stock solution, and the natural pyrethrins were 0. 90 mass% (w/v)) is dissolved in an n-paraffin-based aliphatic saturated hydrocarbon having 11 to 14 carbon atoms (trade name: deotomisole) to prepare an aerosol stock solution of 100 mL. The aerosol stock solution is placed in an aerosol container, a valve portion is attached to the container, and 150 mL of LPG (liquefied petroleum gas) (60% by volume (v / v) based on the total amount of the aerosol composition) is added through the valve portion. The oil-based aerosol agent was prepared by pressure filling. An oily aerosol agent was prepared in the same manner for Example 2 and Comparative Example 5. The following tests were conducted using various aerosol agents.
(1) Insecticidal efficacy test (glass chamber method)
After releasing houseflies (about 25 adult males and females in one group) into a 60 cm cubic (0.216 m 3 ) glass chamber, the test aerosol was sprayed for 1 second, and the number of worms over time was recorded. .. The KT50 value was determined, and the relative efficacy of the aqueous aerosol formulations (Examples 1 and 2 and Comparative Example 5) is shown in Table 2 with the efficacy of the oily aerosol formulation being 1.0. The relative insecticidal efficacy was calculated by the formula of (KT50 value of oily aerosol)/(KT50 value of aqueous aerosol).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　試験例１及び２の結果、本発明の一液型水性エアゾール組成物は除虫菊エキスの溶解性に優れた。また、一液型でエマルジョンの安定性にすぐれ、更に殺虫効力についても対照の油性エアゾール剤と比べて遜色なく実用的であった。なかでも、除虫菊エキスに含まれる（ｈ）天然ピレトリン類と、前記（ｂ）界面活性剤との配合重量比［（ｈ）／（ｂ）］は、０．００５≦［（ｈ）／（ｂ）］≦０．２５の実施例１～７、９、１０および１１は除虫菊エキスのエアゾール組成物に対する溶解性及び殺虫効力において特に優れたものであった。これに対し、比較例１や比較例2のように、界面活性剤が（ｆ）ポリエチレングリコールアルキルエステル類と（ｇ）ソルビタン脂肪酸エステル類の組み合わせでないもの、また比較例３や比較例７のように、界面活性剤が両者の組み合わせであってもその配合重量比［（ｆ）／（ｇ）］が０．５≦［（ｆ）／（ｇ）］≦２．５の範囲を外れるものは、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性が低く、エマルジョンの安定性が不良であった。また噴射剤としてＤＭＥを用いた場合（比較例４）は、エマルジョンの安定性の低下を招いた。さらに、特開２００３－４０７０４で好適とされた界面活性剤に除虫菊エキスを加えた処方（比較例２、比較例６）では、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性において満足のいくものではなかった。これは、特開２００３－４０７０４では、殺虫成分として合成ピレスロイド系化合物が使用されたのに対し、本願で用いる天然産の除虫菊エキスは植物由来の不純物を多く含み、界面活性剤の選定に当たっては、従来の技術を適用することは難しく、高度な適合性が求められたためである。また、エアゾール原液中の水の量を多くした処方（比較例５）では殺虫効力が大幅に低下した。 As a result of Test Examples 1 and 2, the one-component aqueous aerosol composition of the present invention was excellent in the solubility of pyrethrum extract. In addition, it was a one-component type and had excellent emulsion stability, and its insecticidal efficacy was comparable to that of the control oil-based aerosol agent. In particular, the blending weight ratio [(h)/(b)] of (h) natural pyrethrins contained in the pyrethrum extract and the above-mentioned (b) surfactant is 0.005≦[(h)/(b )] Examples 1 to 7, 9, 10 and 11 of ≦ 0.25 were particularly excellent in the solubility and insecticidal efficacy of pyrethrum extract in the aerosol composition. On the other hand, as in Comparative Example 1 and Comparative Example 2, the surfactant is not a combination of (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters, and as in Comparative Example 3 and Comparative Example 7. In addition, even if the surfactant is a combination of the two, the compounding weight ratio [(f) / (g)] is out of the range of 0.5 ≦ [(f) / (g)] ≦ 2.5. The solubility of the pyrethrum extract in the one-component aqueous aerosol composition was low, and the emulsion stability was poor. Further, when DME was used as the propellant (Comparative Example 4), the stability of the emulsion was lowered. Furthermore, in the formulations (Comparative Example 2 and Comparative Example 6) in which the pyrethrum extract was added to the surfactant suitable in JP-A-2003-40704 (Comparative Example 2 and Comparative Example 6), the solubility of the pyrethrum extract in the one-part aqueous aerosol composition was satisfactory. It wasn't something. This is because in Japanese Patent Application Laid-Open No. 2003-40704, a synthetic pyrethroid compound was used as an insecticidal component, whereas the naturally occurring pyrethrum extract used in the present application contains a large amount of plant-derived impurities, and when selecting a surfactant, This is because it is difficult to apply the conventional technique and a high degree of compatibility is required. Moreover, the insecticidal effect was significantly reduced in the formulation (Comparative Example 5) in which the amount of water in the aerosol stock solution was increased.
　本発明は、除虫菊エキスの一液型水性エアゾール組成物に対する溶解性に優れ、一液型水性エアゾール組成物の安定性にも優れ、さらに殺虫効力面にも優れた一液型水性エアゾール組成物であり、除虫菊エキスを含有する水性エアゾール剤として好適に用いられる。 The present invention is a one-component aqueous aerosol composition having excellent solubility in a one-component aqueous aerosol composition of pyrethrum extract, excellent stability of the one-component aqueous aerosol composition, and excellent insecticidal efficacy. And is preferably used as an aqueous aerosol containing pyrethrum extract.

Claims (3)

  1. 　（ａ）除虫菊エキス、（ｂ）界面活性剤、（ｃ）炭素数が８～１６個の脂肪族炭化水素、及び（ｄ）水を含有するエアゾール原液と、（ｅ）噴射剤としてのＬＰＧ（液化石油ガス）とを含有する一液型水性エアゾール組成物であって、
    　前記（ｂ）界面活性剤は、（ｆ）ポリエチレングリコールアルキルエステル類と（ｇ）ソルビタン脂肪酸エステル類を含有し、その配合重量比［（ｆ）／（ｇ）］は０．５≦［（ｆ）／（ｇ）］≦２．５であり、
    　前記（ｄ）水の当該エアゾール原液全体量に対する配合量は１５～５３質量％（ｗ／ｖ）であり、
    　かつ、前記（ｅ）噴射剤の当該一液型水性エアゾール組成物全体量に対する配合量は４０～７０容量％（ｖ／ｖ）である一液型水性エアゾール組成物。     An aerosol stock solution containing (a) an insecticide chrysanthemum extract, (b) a surfactant, (c) an aliphatic hydrocarbon having 8 to 16 carbon atoms, and (d) water, and (e) LPG as a propellant (e) A one-component aqueous aerosol composition containing liquefied petroleum gas).
    The (b) surfactant contains (f) polyethylene glycol alkyl esters and (g) sorbitan fatty acid esters, and the blending weight ratio [(f)/(g)] is 0.5≦[(f )/(G)]≦2.5,
    The blending amount of the (d) water with respect to the total amount of the aerosol stock solution is 15 to 53% by mass (w/v),
    The one-component aqueous aerosol composition, wherein the amount of the (e) propellant is 40 to 70% by volume (v/v) with respect to the total amount of the one-component aqueous aerosol composition.
  2. 　前記（ａ）除虫菊エキスに含まれる（ｈ）天然ピレトリン類と、前記（ｂ）界面活性剤との配合重量比［（ｈ）／（ｂ）］は、０．００５≦［（ｈ）／（ｂ）］≦０．３４である請求項１に記載の一液型水性エアゾール組成物。 The blending weight ratio [(h)/(b)] of the (h) natural pyrethrins contained in the (a) pyrethrum extract to the (b) surfactant is 0.005≦[(h)/( b)]≦0.34, The one-component aqueous aerosol composition according to claim 1.
  3. 　前記（ｂ）界面活性剤は、さらにポリオキシエチレンポリオキシプロピレンアルキルエーテル類を含有する請求項１に記載の一液型水性エアゾール組成物。 The one-component aqueous aerosol composition according to claim 1, wherein the surfactant (b) further contains polyoxyethylene polyoxypropylene alkyl ethers.
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GB1256417A (en) * 1968-05-31 1971-12-08 Johnson & Son Inc S C Pyrethroid insecticide
JPS50117917A (en) * 1974-03-04 1975-09-16
JPS5423123A (en) * 1977-07-20 1979-02-21 Earth Chemical Co One part aqueous aerosol pesticide
JPH06329510A (en) * 1993-05-25 1994-11-29 Earth Chem Corp Ltd Aerosol insecticide and insecticidal method
JP2003040704A (en) * 2001-07-27 2003-02-13 Dainippon Jochugiku Co Ltd Micro-emulsion aerosol composition
CN103141526A (en) * 2013-02-06 2013-06-12 深圳馥稷生物科技有限公司 Botanical insecticide aerosol containing natural pyrethrin and plant essential oil and method
JP2014510106A (en) * 2011-03-24 2014-04-24 エス．シー． ジョンソン アンド サン、インコーポレイテッド Pyrethrin-based repellent

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MY140912A (en) * 2004-07-26 2010-01-29 Du Pont Mixtures of anthranilamide invertebrate pest control agents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1256417A (en) * 1968-05-31 1971-12-08 Johnson & Son Inc S C Pyrethroid insecticide
JPS50117917A (en) * 1974-03-04 1975-09-16
JPS5423123A (en) * 1977-07-20 1979-02-21 Earth Chemical Co One part aqueous aerosol pesticide
JPH06329510A (en) * 1993-05-25 1994-11-29 Earth Chem Corp Ltd Aerosol insecticide and insecticidal method
JP2003040704A (en) * 2001-07-27 2003-02-13 Dainippon Jochugiku Co Ltd Micro-emulsion aerosol composition
JP2014510106A (en) * 2011-03-24 2014-04-24 エス．シー． ジョンソン アンド サン、インコーポレイテッド Pyrethrin-based repellent
CN103141526A (en) * 2013-02-06 2013-06-12 深圳馥稷生物科技有限公司 Botanical insecticide aerosol containing natural pyrethrin and plant essential oil and method

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