WO2018030532A1 - Method for inhibiting penetration of pest repellent into skin and agent for inhibiting penetration of pest repellent into skin - Google Patents

Method for inhibiting penetration of pest repellent into skin and agent for inhibiting penetration of pest repellent into skin Download PDF

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Publication number
WO2018030532A1
WO2018030532A1 PCT/JP2017/029186 JP2017029186W WO2018030532A1 WO 2018030532 A1 WO2018030532 A1 WO 2018030532A1 JP 2017029186 W JP2017029186 W JP 2017029186W WO 2018030532 A1 WO2018030532 A1 WO 2018030532A1
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Prior art keywords
pest repellent
skin
ether
penetration
polyoxypropylene
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PCT/JP2017/029186
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French (fr)
Japanese (ja)
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麻由 川口
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アース製薬株式会社
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Priority to CN201780049350.9A priority Critical patent/CN109843055B/en
Publication of WO2018030532A1 publication Critical patent/WO2018030532A1/en

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    • 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
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring

Definitions

  • the present invention relates to a method for suppressing penetration of a pest repellent into the skin and a penetration inhibitor for penetration of the pest repellent into the skin.
  • various pest repellents have been used to prevent damage from blood-sucking insects such as mosquitoes, abs and bed bugs.
  • various examinations are made in order to improve the feeling of use, reduce irritation, and increase the sustainability of the repellent effect.
  • Patent Document 1 in order to improve the sustainability, dispersibility, storage stability and usability of the pest repellent effect by the pest repellent component, the pore volume is 1 ml / g or less, the average pore diameter is 100 mm or less, and the ratio
  • a pest repellent composition containing silica particles having a surface area of less than 500 m 2 / g is disclosed and described as being used as an aerosol.
  • Patent Document 2 discloses ultraviolet rays in order to prevent deterioration of repellent components caused by exposure to sunlight or the like in a pest repellent for human body containing natural mineral water with improved usability and irritation to the human body.
  • a human pest repellent containing an absorbent is disclosed.
  • the silicic acid anhydride particles are hydrophobic, the silicic acid silicic acid particles settle on the bottom of the container during storage, and the container is shaken and mixed each time during use. The particles must be dispersed.
  • problems such as clogging of the injection port or stem hole or sticking to the injection surface as a lump when a large amount of silica particles are injected In some cases, a desired effect cannot be obtained unless the proper use is made during use.
  • Patent Document 2 the pest repellent for human body of Patent Document 2 is not practical because it is not easy to obtain natural mineral water to be blended and it is difficult to stably supply it.
  • the conventional pest repellent composition and the pest repellent cannot retain a repellent effective amount of the pest repellent on the skin for a long time. Therefore, the persistence of the pest repellent effect of the pest repellent applied to the skin was insufficient.
  • pest repellents such as diet have skin irritation, if the pest repellent penetrates into the skin, it will irritate the skin, and safety when applied to the human body is insufficient. It was.
  • the object of the present invention is to provide a method for suppressing penetration of a pest repellent into the skin in order to improve the sustainability of the pest repellent effect on the skin over a long period of time with less irritation by the drug. There is.
  • the present inventor applied a specific ether compound together with a pest repellent to the skin to suppress the penetration of the pest repellent into the skin, and the pest repellent for a long time.
  • the present inventors have found that it can be retained on the skin surface) and have completed the present invention.
  • a pest repellent which applies to the skin at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether together with the pest repellent A method of suppressing skin penetration.
  • the pest repellent includes N, N-diethyl-m-toluamide, 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) )
  • the pest repellent is N, N-diethyl-m-toluamide, the N, N-diethyl-m-toluamide is 1.5 mg / 100 cm 2 or more and the ether compound is 0.3 mg / 100 cm.
  • a skin pest repellent inhibitor comprising at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
  • ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
  • the penetration inhibitor for skin penetration of the pest repellent according to (6) which is used for suppressing penetration of at least one pest repellent selected from the group consisting of esters into the skin.
  • a pest repellent which applies at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether to the skin together with the pest repellent. A method for suppressing irritation to the skin.
  • At least one ether system selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether By applying the compounds together, the penetration of the pest repellent into the skin can be suppressed. As a result, the pest repellent can be retained on the skin for a long time, and the sustainability of the pest repellent effect on the skin can be improved.
  • the pest repellent effect can be maintained for a long time, and a preparation with less irritation to the human body can be provided. Further, since the penetration of the pest repellent into the skin can be suppressed by the method of the present invention, even when the pest repellent is used at a high concentration, irritation to the skin of the pest repellent can be suppressed, On the other hand, a safer preparation can be provided.
  • FIG. 1 is a schematic diagram of a horizontal diffusion cell used in a skin absorption inhibition test.
  • FIG. 2 is a graph showing the results of Test Example 2.
  • FIG. 3 is a graph showing the results of Test Example 3.
  • the present invention by applying to the skin at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether together with a pest repellent,
  • the present invention provides a method for suppressing penetration of a pest repellent into the skin.
  • the present invention also relates to a pest repellent applied on the skin of at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
  • permeation to the skin is provided.
  • N, N-diethyl-m-toluamide hereinafter referred to as “diet”
  • IR3535 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester
  • IR3535 1-butyl-N-acetyl aminopropionic acid ethyl ester
  • IR3535 1-butyl-N-acetyl aminopropionic acid ethyl ester
  • IR3535 N-butyl-N-acetyl aminopropionic acid ethyl ester
  • icaridin 1 -Piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester
  • p-menthane-3,8-diol 2-ethyl-1,3-hexadiol
  • Citronella peppermint, cedarwood, lavender, tea tree oil, cinnamon bark, camphor, lemongrass, clover, ginger, geranium, bergamont, laurel, pine, red peach, Benny royal, eucalyptus, Indian sedan, etc.
  • Extracted essential oils and extracts, as well as pyrethroids such as pyrethrin, allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, permethrin, ciphenothrin, praretrin, etofenprox, empentrin, transfluthrin, methfluthrin, profluthrin, etc. be able to.
  • pest repellents can be used singly or in combination of two or more, and among these, it is preferable to use Diet, IR3535, and icaridin from the viewpoint of high versatility.
  • the affinity with a drug having a log P value of 1 to 4 when measured at 20 to 25 ° C. is improved. It is known to easily penetrate into the skin. Therefore, a pest repellent having a log P value in the range of 1 to 4 has good affinity with the hydrophobic stratum corneum and easily penetrates into the stratum corneum. Therefore, a pest repellent having a log P value of 1 to 4 and a large amount of penetration into the skin is composed of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether described later.
  • the effect of the present invention that suppresses penetration of a pest repellent into the skin by at least one ether compound selected from the group is more remarkably obtained.
  • the log P value is a coefficient representing the polarity depending on the ease of distribution of the substance into water and octanol as defined in Chemical Reviews vol 71 (6), 525 (1971).
  • the log P value of the drug can be calculated by calculation software (PALAAS: CompDrug Chemistry Ltd.), for example, Diet has LogP of 2, IR3535 has LogP of 1.7, and icaridin has LogP of 2.1. .
  • At least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether (hereinafter referred to as “specific ether”).
  • specific ether polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether
  • the ethylene oxide group or propylene oxide group of oxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether has an action to retain a pest repellent and protects against skin penetration. It is presumed to exert an excellent effect in suppressing the penetration of the agent into the skin.
  • the present invention is a method for suppressing the penetration of a pest repellent into the skin by applying a specific ether compound together with the pest repellent to the skin, and improving the persistence of the pest repellent effect of the pest repellent on the skin Is also provided.
  • the present invention also provides a method for suppressing the penetration of the pest repellent into the skin and the stimulation of the pest repellent on the skin by applying the specific ether compound together with the pest repellent to the skin. .
  • the specific ether compound used in the present invention preferably has a weight average molecular weight of 500 to 10,000. If the weight average molecular weight of the specific ether compound is 500 or more, the desired effect of the present invention is sufficiently obtained, and if it is 10,000 or less, preparation of the preparation becomes easy.
  • the weight average molecular weight of the specific ether compound is more preferably 600 or more, further preferably 650 or more, more preferably 5,000 or less, and further preferably 4,000 or less.
  • the weight average molecular weight can be measured by gel permeation chromatography.
  • the polymerization degree of the specific ether compound is preferably 3 to 200. If the polymerization degree of the specific ether compound is 3 or more, the desired effect of the present invention can be sufficiently obtained, and the specific ether compound having a polymerization degree of 200 or less is preferable because of its high versatility.
  • the degree of polymerization of the specific ether compound is more preferably 5 or more, further preferably 9 or more, more preferably 100 or less, and still more preferably 80 or less. In the case of a copolymer, the sum may be in the above range.
  • the carbon number of the specific ether compound is preferably 10 to 600. If the number of carbon atoms of the specific ether compound is 10 or more, the desired effect of the present invention is sufficiently obtained, and if it is 600 or less, compatibility with various components is increased when a pest repellent composition is obtained. 20 or more are more preferable, as for carbon number of a specific ether type compound, 30 or more are more preferable, 400 or less are more preferable, and 200 or less are still more preferable.
  • the average addition mole number of oxypropylene of the specific ether compound is preferably 3 to 100.
  • polyoxyethylene polyoxypropylene alkyl ether is 5 to 100.
  • the polyoxypropylene diglyceryl ether is 3 to 20, and the polyoxypropylene alkyl ether is 3 to 100.
  • polyoxyethylene polyoxypropylene alkyl ether examples include polyoxyethylene (9) polyoxypropylene (10) butyl ether, polyoxyethylene (17) polyoxypropylene (17) butyl ether, polyoxyethylene (30) polyoxypropylene (30) Butyl ether, polyoxyethylene (37) polyoxypropylene (38) butyl ether, polyoxyethylene (10) polyoxypropylene (8) cetyl ether, polyoxyethylene (20) polyoxypropylene (8) cetyl ether, etc.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the desired effect of the present invention can be sufficiently obtained, and when it is used as a pest repellent composition, the compatibility with various components is high, and further the usability is good. Can do.
  • the average added mole number of oxyethylene is preferably 5 to 100, more preferably 5 to 50.
  • the average added mole number of oxypropylene is preferably 5 to 100, more preferably 5 to 50.
  • the desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
  • polyoxyethylene polyoxypropylene alkyl ether commercially available products can be used.
  • polyoxypropylene diglyceryl ether examples include polyoxypropylene (9) diglyceryl ether and polyoxypropylene (14) diglyceryl ether.
  • the average added mole number of oxypropylene is preferably from 3 to 20, more preferably from 5 to 15. The desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
  • polyoxypropylene diglyceryl ether commercially available products can be used.
  • Examples include “SY-DP14” and “SY-DP9” (both are trade names) manufactured by the company.
  • polyoxypropylene alkyl ether examples include polyoxypropylene (12) butyl ether, polyoxypropylene (52) butyl ether, polyoxypropylene (15) stearyl ether, and the like.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the average number of moles of oxypropylene added is preferably 3 to 100, more preferably 3 to 60. The desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
  • polyoxypropylene alkyl ether commercially available products can be used.
  • the polyoxyethylene polyoxypropylene alkyl ether includes polyoxyethylene (9) polyoxypropylene (10) butyl ether, polyoxyethylene, from the viewpoint of compatibility with various components when making a pest repellent composition.
  • Polyoxypropylene (17) butyl ether, polyoxyethylene (30) polyoxypropylene (30) butyl ether, polyoxyethylene (37) polyoxypropylene (38) butyl ether are preferably used, and polyoxypropylene diglyceryl ether
  • polyoxypropylene (9) diglyceryl ether it is preferable to use polyoxypropylene (12) butyl ether, polyoxypropylene ( It is preferred to use 2) ether.
  • polyoxyethylene polyoxypropylene alkyl ether from the point that the penetration inhibitory effect of the pest repellent into the skin is high.
  • the specific ether compound of the present invention When the specific ether compound of the present invention is applied to the skin together with a pest repellent, it is preferable to use the specific ether compound in an amount of 1 to 300 parts by mass, more preferably 100 parts by mass of the pest repellent.
  • the amount is 3 to 200 parts by mass, more preferably 5 to 100 parts by mass.
  • both the pest repellent and the specific ether compound may be applied simultaneously or separately. From the viewpoint of easy spreading on the entire skin, the stimulation of pest repellents such as diet, etc. being alleviated, and from the viewpoint of simplicity, it is preferable to apply both to the skin at the same time.
  • pest repellents and specific ether compounds When applying pest repellents and specific ether compounds to the skin, for example, pumps, lotions, wet tissues, roll-on agents, coating agents, gels, creams, aerosols, etc. can do.
  • Solvents that can be used include, for example, tap water, purified water, ionic water, and the like, ethyl alcohol, isopropyl alcohol, lauryl alcohol, cetanol, 2-hexyldecanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, lanolin alcohol, and the like.
  • Examples include alcohols, ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,3-pentanediol, glycerol and other polyhydric alcohols, hydrocarbon solvents, and the like.
  • emulsifying / dispersing agent examples include sorbitan trioleate, polyoxyethylene monooleate, polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, decaglycerin mono Surfactant such as oleate, propylene glycol dioleate, polyoxyethylene stearamide, polyoxyethylene lauryl ether phosphate, glycerin fatty acid ester, stearyl alcohol, polyvinyl pyrrolidone, lanolin fatty acid, polyisoethylene stearate polyoxyethylene glyceryl, lower alcohol And polyhydric alcohols.
  • sorbitan trioleate polyoxyethylene monooleate
  • polyoxyethylene alkyl ether polyoxyethylene nonylphenyl ether
  • polyoxyethylene hydrogenated castor oil polyoxyethylene alkyl ether
  • decaglycerin mono Surfactant such as oleate, propylene glyco
  • the adherence amount of the diet to the skin is 1.5 mg / 100 cm 2 or more, more preferably 5.0 mg. / 100 cm 2 or more, and the specific ether compound is preferably applied so that the amount of the specific ether compound attached to the skin is 0.3 mg / 100 cm 2 or more.
  • a diet with an amount of 1.5 to 150 mg / 100 cm 2 and the specific ether compound of the present invention with an amount of 0.3 to 450 mg / 100 cm 2 .
  • a coating agent, a roll-on agent or a wet tissue agent for example, when an aerosol agent or a pump agent is used when applied to the skin, a nozzle, a valve, an injection pressure, etc. are adjusted, a coating agent, a roll-on agent or a wet tissue agent.
  • the adhesion amount of the pest repellent and the specific ether compound to the skin may be adjusted by adjusting the shape of the coated surface or the material property of the coated part.
  • the aerosol container may be pressurized and filled so that the propellant is 40 to 95 v / v% with respect to the whole preparation.
  • the propellant for example, liquefied petroleum gas, dimethyl ether, alternative chlorofluorocarbon, compressed gas (carbon dioxide, nitrogen), and a mixture thereof can be used.
  • the basis weight of the support is preferably 20 to 80 g / m 2 .
  • the basis weight of the support is 20 to 80 g / m 2, it is possible to incorporate, hold, apply and impregnate a desired pest repellent and a specific ether compound.
  • the pest repellent at 70 to 300 ml / m 2 on a support having a thickness of about 0.1 to 5 mm.
  • a support having a thickness of about 0.1 to 5 mm By holding the pest repellent on the support at 70 to 300 ml / m 2 , it is possible to incorporate, hold, apply and impregnate the desired pest repellent and the ether compound of the present invention.
  • woven fabric such as flannel, cotton, silk, polyester, nylon, or the like made from these materials
  • non-woven fabric such as polyester, polyolefin, nylon, cotton, rayon, vinylon, cellulose, or the like made from these materials
  • a sheet-like resin foam obtained by foaming polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like can be used.
  • an arbitrary amount of powder for example, an arbitrary amount of powder, a fragrance component, a sterilizing / preserving component, a moisturizing component, an increasing amount, for the purpose of improving the feeling of use, increasing the repellent effect of pests, or imparting a bactericidal effect.
  • a viscosity agent, a lubricant, a solubilizer, a pH adjuster, a stabilizer and the like can be contained.
  • inorganic powder such as hydrophobic silica, calcium silicate, diatomaceous earth, high purity silica, anhydrous silicic acid, talc, calcium carbonate, magnesium stearate, acid clay, white carbon, pearlite; octenyl succinic acid corn starch ester aluminum, etc.
  • alkenyl succinate starch Natural powders such as silk powder; powders such as resins such as nylon and polypropylene; fragrance ingredients such as menthol, mint oil, mint oil; phenol, paraoxybenzoic acid ester, salicylic acid and salts thereof
  • Bactericidal and antiseptic ingredients such as benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, phenoxyethanol; sodium hyaluronate, ceramide, collagen, placenta extract, milk protein, soy Moisturizing ingredients (wetting agents) such as bit, glycerin, ascorbic acid (vitamin C derivative), N-stearoyl phytosphingodine, dipotassium glycyrrhizinate, meadowfoam oil, natural vitamin E; carboxyvinyl polymer, 3-octadecyloxy-2- Thickeners such as hydroxypropyl 2-hydroxypropylmethylcellulose, acrylic acid / alky
  • Pigment components such as safflower; octamethyltrisiloxane, decamethyltetrasiloxane, methylpolysiloxane, polyoxyethylene / methylpolysiloxane copolymer Lubricants; citric acid, sodium citrate, arginine, pH adjusting agents such as triisopropanolamine; glycerin mono-2-ethylhexyl ether, stabilizing agents such as diethylenetriaminepentaacetic acid pentasodium solution and the like.
  • higher fatty acid esters such as isopropyl myristate and hexyl laurate; aloe, peach, touki, cordyceps, tomato, carrot, boucle, red grape, ashitaba, artea, arnica, diatom, cucumber, tea, burdock, shiitake, jiou, taiso,
  • plant extracts such as strawberry tea, phan, loofah, button, lily, apple, litchi; silicone, etc.
  • Examples of the pests that can be repelled in the present invention include various biting pests such as mosquitoes, flyfish, house dust mites, fleas, sand flies, bed bugs, mountain bills, ticks, bees, ants, abs, and tsutsugamushi.
  • biting pests such as mosquitoes, flyfish, house dust mites, fleas, sand flies, bed bugs, mountain bills, ticks, bees, ants, abs, and tsutsugamushi.
  • the present invention relates to at least one ether system selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether in order to suppress penetration of the pest repellent into the skin.
  • the compound is applied to the skin together with a pest repellent, and relates to the use of the specific ether compound.
  • the persistence of the pest repellent effect is improved and the irritation to the skin is suppressed.
  • a pest repellent composition is provided.
  • the insect repellent examples include various compounds as described above.
  • the content of the pest repellent is usually 0.1 to 99.5 w / v%, more preferably 0.1 to 50 w / v%, still more preferably 0.5 to 50 w / v based on the pest repellent composition. It is v%, particularly preferably 1 to 30 w / v%.
  • the content of the pest repellent is 1 w / v% or more, the sustained effect is remarkable, and when it is 30 w / v% or less, the stickiness is small.
  • the effective amount of the specific ether compound is preferably 0.1 to 99.5 w / v%, more preferably 0.1 to 50 w / v%, still more preferably 0.5 to 30 w / v with respect to the pest repellent composition. It is v%, particularly preferably 0.5 to 10 w / v%.
  • the content of the specific ether compound is 0.5 w / v% or more, the sustained effect is remarkable, and when it is 10 w / v% or less, the stickiness is small.
  • the content of the specific ether compound is preferably 1 to 300 parts by mass when the content of the pest repellent is 100 parts by mass, and preferably 5 to 100 parts by mass. More preferred. By being the said range, the effect which suppresses the penetration
  • the pest repellent composition can be used as various preparations such as a pump agent, a lotion agent, a wet tissue agent, a roll-on agent, a coating agent, a gel agent, a cream agent and an aerosol agent as described above.
  • the preparation is performed using a known solvent, an emulsifying / dispersing agent, a propellant, etc. as described above, and if necessary, a nonwoven fabric, an actuator, What is necessary is just to combine with an applicator, a pump apparatus, an aerosol apparatus, etc., and to make it a desired formulation form.
  • the present invention also relates to penetration of a pest repellent into the skin, comprising at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
  • An inhibitor is provided. Since this penetration inhibitor contains the specific ether compound of the present invention, the penetration of the pest repellent into the skin can be suppressed, and the pest repellent can be retained in the epidermis for a longer time.
  • Example 1 Skin absorption inhibition test> (Examples 1 to 7, Comparative Examples 1 to 3, Reference Example 1) According to the formulation shown in Table 1, each component was mixed with stirring to prepare a pest repellent composition. Using the obtained pest repellent composition, the amount of diet (log P: 2) remaining on the skin was measured according to the following test method.
  • the horizontal diffusion cell 10 is a device in which a receptor cell 2 and a donor cell 11 covered with a water jacket 4 are arranged in a horizontal state through a sample film (skin 1), and the receptor cell 2 and the donor cell 11 are joined to each other. Can be separated. In this test, the donor cell 11 side is used for fixing the sample film.
  • Mouse skin 1 (lab skin, obtained from Hoshino Experimental Animal Breeding Co., Ltd.) was attached to the horizontal diffusion cell 10 so that the dermis side of the skin 1 was positioned on the receptor cell 2 side. 2. About 45 ⁇ L of the prepared insect repellent composition was treated on the horny layer side (4.9 cm 2 ) of the skin 1, covered with aluminum foil 8, and the skin 1 was fixed with the tightening knob 6. 3. Receptor cell 2 was filled with 50 mL of physiological saline 9 and the cell was filled with physiological saline 9. 4). During the test, the receptor cell 2 stirs the physiological saline in the cell with a stirrer 3, and hot water at 37 ° C.
  • the temperature in the receptor cell 2 was kept constant at 37 ° C. 5). From the time when the temperature in the receptor cell 2 reached 37 ° C., 3 mL of physiological saline 9 was sampled from the sampling port 7 of the receptor cell 2 every hour. Thereafter, the same amount of physiological saline was returned to the receptor cell 2 to keep the liquid volume constant. 6). The amount of diet in the sampling solution was measured by high performance liquid chromatography (HPLC).
  • HPLC high performance liquid chromatography
  • Table 2 shows the results obtained by the above test. If the residual amount on the skin is 0.05 mg / cm 2 or more, it can be determined that it has a repellent effect.
  • Example 2 Blood absorption prevention test> (Examples 8 to 9, Comparative Examples 4 to 5) According to the formulation shown in Table 3, each component was mixed under stirring to prepare a pest repellent composition. Using the obtained pest repellent composition, the repellent rate was measured according to the following test method.
  • the test was conducted according to the following procedure. 1. About 50 female Aedes albopictus were released in a metal cage (length 25 cm ⁇ width 25 cm ⁇ height 25 cm) equipped with an openable and closable arm insertion window (about 113 cm 2 ). 2. The prepared pest repellent composition was applied to the back of the subject's hand, and after application, a rubber glove with the back of the hand cut into a substantially square shape of 5 cm ⁇ 5 cm was worn. The coating amount was 1.34 ⁇ L / cm 2 . 3.
  • the repellent rate was calculated by the following formula from the number of landings of Aedes albopictus in the case of treating the pest repellent composition (treated group) and the number of Aedes albopictus in the untreated group.
  • Repellent rate (%) (No treatment area landing number-Treatment area landing number) / No treatment area landing number x 100
  • Example 3 Blood absorption prevention test> (Example 10, Comparative Examples 6-7) According to the formulation shown in Table 5, each component was mixed with stirring to prepare a pest repellent composition. Comparative Example 6 has the same formulation as Comparative Example 5 in Test Example 2. Using the obtained pest repellent composition, the repellent rate was measured according to the following test method.
  • ⁇ Test method The test was conducted according to the following procedure. 1. About 50 female Aedes albopictus were released in a metal cage (length 25 cm ⁇ width 25 cm ⁇ height 25 cm) equipped with an openable and closable arm insertion window (about 113 cm 2 ). 2. The prepared pest repellent composition was applied to the back of the subject's hand, and after application, a rubber glove with the back of the hand cut into a substantially square shape of 5 cm ⁇ 5 cm was worn. The coating amount was 0.80 ⁇ L / cm 2 . 3.
  • the repellent rate was calculated by the following formula from the number of landings of Aedes albopictus in the case of treating the pest repellent composition (treated group) and the number of Aedes albopictus in the untreated group.
  • Repellent rate (%) (No treatment area landing number-Treatment area landing number) / No treatment area landing number x 100
  • Example 10 has a duration of 9 hours for which the repelling rate is 80% or more, 7 hours than Comparative Example 6 having the same diet content, and a repelling rate of 80% or more. Was able to continue. Further, in Example 10, the duration time in which the repelling rate was 80% or more was equal to or more than that in Comparative Example 7 in which the diet content was tripled. From these results, it was found that according to the present invention, the pest repellent effect can be maintained for a long time even when the pest repellent is used at a low concentration.

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Abstract

The present invention address the problem of providing a method for inhibiting penetration of a pest repellent into the skin in order to reduce irritation caused by chemical agents and to improve the persistence of a pest-repelling effect on the skin over a long period of time. In this method for inhibiting penetration of a pest repellent into the skin, at least one ether-based compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether, and polyoxypropylene alkyl ether is applied to the skin with a pest repellent.

Description

害虫忌避剤の皮膚への浸透を抑制する方法及び害虫忌避剤の皮膚への浸透抑制剤Method for inhibiting penetration of pest repellent into skin and penetration inhibitor for pest repellent into skin
　本発明は、害虫忌避剤の皮膚への浸透を抑制する方法及び害虫忌避剤の皮膚への浸透抑制剤に関する。 The present invention relates to a method for suppressing penetration of a pest repellent into the skin and a penetration inhibitor for penetration of the pest repellent into the skin.
　従来、蚊をはじめとしたアブ、トコジラミなどの吸血昆虫からの被害を防ぐために、各種の害虫忌避剤が用いられてきた。これらの害虫忌避剤については、使用感の向上や刺激性の低減、忌避効果の持続性を高めるために各種検討がなされている。 Conventionally, various pest repellents have been used to prevent damage from blood-sucking insects such as mosquitoes, abs and bed bugs. About these pest repellents, various examinations are made in order to improve the feeling of use, reduce irritation, and increase the sustainability of the repellent effect.
　例えば、特許文献１には、害虫忌避成分による害虫忌避効果の持続性、分散性、保存安定性及び使用感を向上させるために、細孔容積１ｍｌ／ｇ以下、平均細孔径１００Å以下、かつ比表面積が５００ｍ２／ｇ未満の無水ケイ酸粒子が配合された害虫忌避組成物が開示され、エアゾールとして用いられることが記載されている。
　また、特許文献２には、使用感ならびに人体への刺激性が改善された天然ミネラル水配合の人体用害虫忌避剤において、日光等に曝されることによる忌避成分の劣化を防止するために紫外線吸収剤を含有した人体用害虫忌避剤が開示されている。 For example, in Patent Document 1, in order to improve the sustainability, dispersibility, storage stability and usability of the pest repellent effect by the pest repellent component, the pore volume is 1 ml / g or less, the average pore diameter is 100 mm or less, and the ratio A pest repellent composition containing silica particles having a surface area of less than 500 m 2 / g is disclosed and described as being used as an aerosol.
In addition, Patent Document 2 discloses ultraviolet rays in order to prevent deterioration of repellent components caused by exposure to sunlight or the like in a pest repellent for human body containing natural mineral water with improved usability and irritation to the human body. A human pest repellent containing an absorbent is disclosed.
日本国特開平９－２０８４０６号公報Japanese Unexamined Patent Publication No. 9-208406 日本国特開２００９－１２６８０４号公報Japanese Unexamined Patent Publication No. 2009-126804
　しかしながら、特許文献１の害虫忌避組成物においては、無水ケイ酸粒子は疎水性であるため、保管中に無水ケイ酸粒子が容器底部に沈降し、使用時にはその都度容器を振り混ぜて無水ケイ酸粒子を分散させなくてはならない。エアゾールの場合、容器を振り混ぜないで使用した場合には、無水ケイ酸粒子が多量に噴射されてしまうと噴射口やステム孔等に詰まったり、噴射面に塊で付着してしまう等の問題が生じる場合があるので、使用時に適切な使い方をしなければ所望の効果を得ることができない。 However, in the pest repellent composition of Patent Document 1, since the silicic acid anhydride particles are hydrophobic, the silicic acid silicic acid particles settle on the bottom of the container during storage, and the container is shaken and mixed each time during use. The particles must be dispersed. In the case of aerosol, if the container is used without shaking, problems such as clogging of the injection port or stem hole or sticking to the injection surface as a lump when a large amount of silica particles are injected In some cases, a desired effect cannot be obtained unless the proper use is made during use.
　また、特許文献２の人体用害虫忌避剤においては、配合する天然ミネラル水の入手が容易とは言えず、安定して供給しづらいことから実用的ではない。 In addition, the pest repellent for human body of Patent Document 2 is not practical because it is not easy to obtain natural mineral water to be blended and it is difficult to stably supply it.
　また、有効成分である害虫忌避剤は皮膚内部へ浸透しやすいため、従来の害虫忌避組成物や害虫忌避剤では忌避有効量の害虫忌避剤を長時間に亘り皮膚上に滞留させることができない。そのため、皮膚に適用した害虫忌避剤の害虫忌避効果の持続性は不十分なものであった。さらに、ディート等の害虫忌避剤は皮膚刺激性を有するため、害虫忌避剤が皮膚内部へ浸透すると、皮膚に対して刺激を与えることになり、人体に適用する際の安全性は不十分であった。 In addition, since the pest repellent which is an active ingredient easily penetrates into the skin, the conventional pest repellent composition and the pest repellent cannot retain a repellent effective amount of the pest repellent on the skin for a long time. Therefore, the persistence of the pest repellent effect of the pest repellent applied to the skin was insufficient. In addition, since pest repellents such as diet have skin irritation, if the pest repellent penetrates into the skin, it will irritate the skin, and safety when applied to the human body is insufficient. It was.
　そこで、本発明の課題は、薬剤による刺激が少なく、長時間に亘り、皮膚上における害虫忌避効果の持続性を向上させるために、害虫忌避剤の皮膚内部への浸透を抑制する方法を提供することにある。 Therefore, the object of the present invention is to provide a method for suppressing penetration of a pest repellent into the skin in order to improve the sustainability of the pest repellent effect on the skin over a long period of time with less irritation by the drug. There is.
　本発明者は鋭意研究を重ねた結果、特定のエーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚内部への浸透を抑え、長時間に亘り害虫忌避剤を表皮（皮膚表面）に滞留させることができることを見出し、本発明を完成するに至った。 As a result of intensive research, the present inventor applied a specific ether compound together with a pest repellent to the skin to suppress the penetration of the pest repellent into the skin, and the pest repellent for a long time. The present inventors have found that it can be retained on the skin surface) and have completed the present invention.
　すなわち本発明は以下の通りである。
（１）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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用する害虫忌避剤の皮膚への浸透を抑制する方法。
（２）前記害虫忌避剤が、Ｎ，Ｎ－ジエチル－ｍ－トルアミド、３－（Ｎ－ｎ－ブチル－Ｎ－アセチル）アミノプロピオン酸エチルエステル及び１－ピペリジンカルボン酸２－（２－ヒドロキシエチル）－１－メチルプロピルエステルからなる群から選択される少なくとも１つである、前記（１）に記載の害虫忌避剤の皮膚への浸透を抑制する方法。
（３）前記エーテル系化合物のオキシプロピレンの平均付加モル数が、３～１００である、前記（１）又は（２）に記載の害虫忌避剤の皮膚への浸透を抑制する方法。
（４）前記害虫忌避剤１００質量部に対して、前記エーテル系化合物を１～３００質量部の範囲で使用する、前記（１）～（３）のいずれか１つに記載の害虫忌避剤の皮膚への浸透を抑制する方法。
（５）前記害虫忌避剤が、Ｎ，Ｎ－ジエチル－ｍ－トルアミドであり、前記Ｎ，Ｎ－ジエチル－ｍ－トルアミドを１．５ｍｇ／１００ｃｍ２以上かつ前記エーテル系化合物を０．３ｍｇ／１００ｃｍ２以上となる付着量で用いる、前記（１）～（４）のいずれか１つに記載の害虫忌避剤の皮膚への浸透を抑制する方法。
（６）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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物からなる害虫忌避剤の皮膚への浸透抑制剤。
（７）Ｎ，Ｎ－ジエチル－ｍ－トルアミド、３－（Ｎ－ｎ－ブチル－Ｎ－アセチル）アミノプロピオン酸エチルエステル及び１－ピペリジンカルボン酸２－（２－ヒドロキシエチル）－１－メチルプロピルエステルからなる群から選択される少なくとも１つの害虫忌避剤の皮膚への浸透を抑制するために用いられる、前記（６）に記載の害虫忌避剤の皮膚への浸透抑制剤。
（８）オキシプロピレンの平均付加モル数が３～１００である、前記（６）又は（７）に記載の害虫忌避剤の皮膚への浸透抑制剤。
（９）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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用する害虫忌避剤の皮膚に対する刺激を抑制する方法。 That is, the present invention is as follows.
(1) A pest repellent which applies to the skin at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether together with the pest repellent A method of suppressing skin penetration.
(2) The pest repellent includes N, N-diethyl-m-toluamide, 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) ) A method for suppressing penetration of the pest repellent as described in (1) above, which is at least one selected from the group consisting of -1-methylpropyl ester.
(3) The method for suppressing penetration of a pest repellent into the skin according to the above (1) or (2), wherein the ether compound has an average addition mole number of oxypropylene of 3 to 100.
(4) The pest repellent according to any one of (1) to (3), wherein the ether compound is used in an amount of 1 to 300 parts by mass with respect to 100 parts by mass of the pest repellent. A method of suppressing skin penetration.
(5) The pest repellent is N, N-diethyl-m-toluamide, the N, N-diethyl-m-toluamide is 1.5 mg / 100 cm 2 or more and the ether compound is 0.3 mg / 100 cm. A method for suppressing penetration of a pest repellent according to any one of (1) to (4), which is used in an adhesion amount of 2 or more, into the skin.
(6) A skin pest repellent inhibitor comprising at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
(7) N, N-diethyl-m-toluamide, 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl The penetration inhibitor for skin penetration of the pest repellent according to (6), which is used for suppressing penetration of at least one pest repellent selected from the group consisting of esters into the skin.
(8) The pest repellent penetration inhibitor for skin according to (6) or (7), wherein the average added mole number of oxypropylene is 3 to 100.
(9) A pest repellent which applies at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether to the skin together with the pest repellent. A method for suppressing irritation to the skin.
　本発明によれば、害虫忌避剤を皮膚に適用する際に、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を合わせて適用することで、害虫忌避剤の皮膚内部への浸透を抑えることができる。その結果、害虫忌避剤を皮膚上に長時間に亘り滞留させることが可能となり、皮膚上における害虫忌避効果の持続性を向上させることができる。 According to the present invention, when applying the pest repellent to the skin, at least one ether system selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether By applying the compounds together, the penetration of the pest repellent into the skin can be suppressed. As a result, the pest repellent can be retained on the skin for a long time, and the sustainability of the pest repellent effect on the skin can be improved.
　さらに、害虫忌避剤を低濃度で用いても害虫忌避効果を長時間持続させることができ、人体への刺激の少ない製剤を提供することができる。また、本発明の方法により害虫忌避剤の皮膚内部への浸透を抑えることができるので、害虫忌避剤を高濃度で用いた場合でも害虫忌避剤の皮膚に対する刺激を抑制することができ、人体に対してより安全性が高い製剤を提供することができる。 Furthermore, even if a pest repellent is used at a low concentration, the pest repellent effect can be maintained for a long time, and a preparation with less irritation to the human body can be provided. Further, since the penetration of the pest repellent into the skin can be suppressed by the method of the present invention, even when the pest repellent is used at a high concentration, irritation to the skin of the pest repellent can be suppressed, On the other hand, a safer preparation can be provided.
図１は、皮膚吸収抑制試験に用いた水平型拡散セルの模式図である。FIG. 1 is a schematic diagram of a horizontal diffusion cell used in a skin absorption inhibition test. 図２は、試験例２の結果を示すグラフである。FIG. 2 is a graph showing the results of Test Example 2. 図３は、試験例３の結果を示すグラフである。FIG. 3 is a graph showing the results of Test Example 3.
　以下、本発明をさらに詳細に説明する。
　尚、本明細書において、質量で表される全ての百分率や部は、重量で表される百分率や部と同様である。 Hereinafter, the present invention will be described in more detail.
In the present specification, all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.
　本発明は、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚への浸透を抑制する方法を提供するものである。また、本発明は、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物の、皮膚上に適用した害虫忌避剤の皮膚への浸透を抑制させるための使用方法を提供するものである。 The present invention, by applying to the skin at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether together with a pest repellent, The present invention provides a method for suppressing penetration of a pest repellent into the skin. The present invention also relates to a pest repellent applied on the skin of at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether. The use method for suppressing the osmosis | permeation to the skin is provided.
　本発明の害虫忌避剤としては、刺咬性害虫に対して忌避作用又は吸血阻害作用を有する、合成又は天然の各種化合物を用いることができる。例えば、Ｎ，Ｎ－ジエチル－ｍ－トルアミド（以下「ディート」と称する。）、３－（Ｎ－ｎ－ブチル－Ｎ－アセチル）アミノプロピオン酸エチルエステル（以下「ＩＲ３５３５」と称する。）、１－ピペリジンカルボン酸２－（２－ヒドロキシエチル）－１－メチルプロピルエステル（以下「イカリジン」と称する。）、ｐ－メンタン－３，８－ジオール、２－エチル－１，３－ヘキサジオール、ブチル３，４－ジヒドロ－２，２－ジメチル－４－オキソ－２Ｈ－ピラン－６－カルボキシレート、ｎ－ヘキシルトリエチレングリコールモノエーテル、メチル６－ｎ－ペンチル－シクロヘキセン－１－カルボキシレート、ジメチルフタレート、ユーカリプトール、メントール、酢酸メンチル、α－ピネン、ゲラニオール、シトロネラール、シトロネロール、シトラール、ターピネオール、カンファー、リナロール、テルペノール、カルボン、フタル酸ジオクチル、フタル酸ジブチル、ナフタレンなどが挙げられる。 As the pest repellent of the present invention, various synthetic or natural compounds having a repellent action or blood sucking inhibitory action against biting pests can be used. For example, N, N-diethyl-m-toluamide (hereinafter referred to as “diet”), 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester (hereinafter referred to as “IR3535”), 1 -Piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester (hereinafter referred to as "icaridin"), p-menthane-3,8-diol, 2-ethyl-1,3-hexadiol, butyl 3,4-dihydro-2,2-dimethyl-4-oxo-2H-pyran-6-carboxylate, n-hexyltriethylene glycol monoether, methyl 6-n-pentyl-cyclohexene-1-carboxylate, dimethyl phthalate , Eucalyptol, menthol, menthyl acetate, α-pinene, geraniol, citronellal, Roneroru, citral, terpineol, camphor, linalool, terpenols, carboxylic, dioctyl phthalate, dibutyl phthalate, and naphthalene.
　この他にも、例えば、シトロネラ、ペパーミント、シダーウッド、ラベンダー、ティートゥリーオイル、桂皮、樟脳、レモングラス、クローバ、タチジャコウソウ、ジェラニウム、ベルガモント、月桂樹、松、アカモモ、ベニーロイアル、ユーカリ、インドセダンなどから抽出される精油やエキス、さらには、ピレトリン、アレスリン、フタルスリン、レスメトリン、フラメトリン、フェノトリン、ペルメトリン、シフェノトリン、プラレトリン、エトフェンプロックス、エムペントリン、トランスフルスリン、メトフルトリン、プロフルトリンなどのピレスロイド系化合物などを用いることができる。 In addition, for example, Citronella, peppermint, cedarwood, lavender, tea tree oil, cinnamon bark, camphor, lemongrass, clover, ginger, geranium, bergamont, laurel, pine, red peach, Benny royal, eucalyptus, Indian sedan, etc. Extracted essential oils and extracts, as well as pyrethroids such as pyrethrin, allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, permethrin, ciphenothrin, praretrin, etofenprox, empentrin, transfluthrin, methfluthrin, profluthrin, etc. be able to.
　これらの害虫忌避剤は、１種または２種以上を組み合わせて用いることができ、これらの中でも汎用性が高いという観点から、ディート、ＩＲ３５３５、イカリジンを用いることが好ましい。 These pest repellents can be used singly or in combination of two or more, and among these, it is preferable to use Diet, IR3535, and icaridin from the viewpoint of high versatility.
　なお、皮膚表皮の表層である角層は脂溶性が高く疎水表面であるため、２０～２５℃で測定した際のｌｏｇＰ値が１～４である薬剤との親和性が良くなり、薬剤が皮膚へ浸透しやすくなることが知られている。そのため、ｌｏｇＰ値が１～４の範囲にある害虫忌避剤は、疎水性の角層との親和性が良く、角層内に浸透しやすい。
　したがって、ｌｏｇＰ値が１～４であり、皮膚への浸透量が多い害虫忌避剤である程、後述する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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物による害虫忌避剤の皮膚への浸透を抑制する本発明の効果がより顕著に得られる。 Since the stratum corneum, which is the surface layer of the skin epidermis, has a high lipid solubility and a hydrophobic surface, the affinity with a drug having a log P value of 1 to 4 when measured at 20 to 25 ° C. is improved. It is known to easily penetrate into the skin. Therefore, a pest repellent having a log P value in the range of 1 to 4 has good affinity with the hydrophobic stratum corneum and easily penetrates into the stratum corneum.
Therefore, a pest repellent having a log P value of 1 to 4 and a large amount of penetration into the skin is composed of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether described later. The effect of the present invention that suppresses penetration of a pest repellent into the skin by at least one ether compound selected from the group is more remarkably obtained.
　なお、本発明において、ｌｏｇＰ値とは、Ｃｈｅｍｉｃａｌ　Ｒｅｖｉｅｗｓ　ｖｏｌ７１（６），５２５（１９７１）などで定義されている水とオクタノールへの物質の分配のしやすさにより、極性をあらわす係数である。薬剤のｌｏｇＰ値は、計算ソフト（ＰＡＬＡＡＳ：ＣｏｍｐＤｒｕｇ　Ｃｈｅｍｉｓｔｒｙ　Ｌｔｄ．製）にて算出することができ、例えば、ディートはＬｏｇＰが２、ＩＲ３５３５はＬｏｇＰが１．７、イカリジンはＬｏｇＰが２．１である。 In the present invention, the log P value is a coefficient representing the polarity depending on the ease of distribution of the substance into water and octanol as defined in Chemical Reviews vol 71 (6), 525 (1971). The log P value of the drug can be calculated by calculation software (PALAAS: CompDrug Chemistry Ltd.), for example, Diet has LogP of 2, IR3535 has LogP of 1.7, and icaridin has LogP of 2.1. .
　本発明では、前記害虫忌避剤とともに、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物（以下、「特定エーテル系化合物」ともいう。）を皮膚に適用する。前記特定エーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚内部への浸透を抑えることができる。 In the present invention, together with the pest repellent, at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether (hereinafter referred to as “specific ether”). Is also applied to the skin. By applying the specific ether compound together with the pest repellent to the skin, the penetration of the pest repellent into the skin can be suppressed.
　特定エーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚内部への浸透を抑えることができる作用機序は明らかではないが、本発明者の種々の検討の結果、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルのエチレンオキシド基もしくはプロピレンオキシド基が害虫忌避剤を保持する作用を有し、皮膚への浸透を防御するため、害虫忌避剤の皮膚への浸透抑制に優れた効果を発揮すると推測される。 Although the action mechanism that can suppress the penetration of the pest repellent into the skin by applying the specific ether compound together with the pest repellent to the skin is not clear, as a result of various studies by the present inventors, The ethylene oxide group or propylene oxide group of oxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether has an action to retain a pest repellent and protects against skin penetration. It is presumed to exert an excellent effect in suppressing the penetration of the agent into the skin.
　特定エーテル系化合物を皮膚に適用することにより害虫忌避剤の皮膚内部への浸透を抑えることができるので、害虫忌避剤をより長時間皮膚上に滞留させることができ、その結果皮膚上における害虫忌避剤の害虫忌避効果の持続性を向上させることができる。したがって本発明は、特定エーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚への浸透を抑制し、皮膚上における害虫忌避剤の害虫忌避効果の持続性を向上させる方法も提供するものである。 By applying specific ether compounds to the skin, the penetration of the pest repellent into the skin can be suppressed, so that the pest repellent can stay on the skin for a longer time, and as a result, pest repellent on the skin The durability of the pest repellent effect of the agent can be improved. Therefore, the present invention is a method for suppressing the penetration of a pest repellent into the skin by applying a specific ether compound together with the pest repellent to the skin, and improving the persistence of the pest repellent effect of the pest repellent on the skin Is also provided.
　また、特定エーテル系化合物を皮膚に適用することにより害虫忌避剤の皮膚内部への浸透を抑えることができるので、害虫忌避剤の皮膚に対する刺激を抑制することができる。したがって本発明は、特定エーテル系化合物を害虫忌避剤とともに皮膚に適用することにより、害虫忌避剤の皮膚への浸透を抑制し、害虫忌避剤の皮膚に対する刺激を抑制する方法も提供するものである。 Moreover, since the penetration of the pest repellent into the skin can be suppressed by applying the specific ether compound to the skin, irritation to the skin of the pest repellent can be suppressed. Therefore, the present invention also provides a method for suppressing the penetration of the pest repellent into the skin and the stimulation of the pest repellent on the skin by applying the specific ether compound together with the pest repellent to the skin. .
　本発明で用いる特定エーテル系化合物は、重量平均分子量が５００～１０,０００であることが好ましい。特定エーテル系化合物の重量平均分子量が５００以上であれば本発明の所望の効果が十分に得られ、１０，０００以下であると製剤調製が容易となる。特定エーテル系化合物の重量平均分子量は、６００以上がより好ましく、６５０以上が更に好ましく、また、５，０００以下がより好ましく、４，０００以下が更に好ましい。
　重量平均分子量は、ゲルパーミエーションクロマトグラフィーで測定することができる。 The specific ether compound used in the present invention preferably has a weight average molecular weight of 500 to 10,000. If the weight average molecular weight of the specific ether compound is 500 or more, the desired effect of the present invention is sufficiently obtained, and if it is 10,000 or less, preparation of the preparation becomes easy. The weight average molecular weight of the specific ether compound is more preferably 600 or more, further preferably 650 or more, more preferably 5,000 or less, and further preferably 4,000 or less.
The weight average molecular weight can be measured by gel permeation chromatography.
　また、特定エーテル系化合物の重合度は、３～２００であることが好ましい。特定エーテル系化合物の重合度が３以上であれば本発明の所望の効果が十分に得られ、重合度が２００以下の特定エーテル系化合物は汎用性が高いため好ましい。特定エーテル系化合物の重合度は、５以上がより好ましく、９以上が更に好ましく、また、１００以下がより好ましく、８０以下が更に好ましい。なお、共重合体の場合は、総和が上記範囲であればよい。 The polymerization degree of the specific ether compound is preferably 3 to 200. If the polymerization degree of the specific ether compound is 3 or more, the desired effect of the present invention can be sufficiently obtained, and the specific ether compound having a polymerization degree of 200 or less is preferable because of its high versatility. The degree of polymerization of the specific ether compound is more preferably 5 or more, further preferably 9 or more, more preferably 100 or less, and still more preferably 80 or less. In the case of a copolymer, the sum may be in the above range.
　また、特定エーテル系化合物の炭素数は、１０～６００であることが好ましい。特定エーテル系化合物の炭素数が１０以上であれば本発明の所望の効果が十分に得られ、６００以下であると害虫忌避組成物とする際に各種成分との相溶性が高くなる。特定エーテル系化合物の炭素数は、２０以上がより好ましく、３０以上が更に好ましく、また、４００以下がより好ましく、２００以下が更に好ましい。 The carbon number of the specific ether compound is preferably 10 to 600. If the number of carbon atoms of the specific ether compound is 10 or more, the desired effect of the present invention is sufficiently obtained, and if it is 600 or less, compatibility with various components is increased when a pest repellent composition is obtained. 20 or more are more preferable, as for carbon number of a specific ether type compound, 30 or more are more preferable, 400 or less are more preferable, and 200 or less are still more preferable.
　また、特定エーテル系化合物のオキシプロピレンの平均付加モル数は、３～１００であることが好ましい。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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルのそれぞれのオキシプロピレンの平均付加モル数の好適な範囲としては、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は５～１００であり、ポリオキシプロピレンジグリセリルエーテルは３～２０であり、ポリオキシプロピレンアルキルエーテルは３～１００である。 The average addition mole number of oxypropylene of the specific ether compound is preferably 3 to 100. As a preferable range of the average addition mole number of oxypropylene of each of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether is 5 to 100. The polyoxypropylene diglyceryl ether is 3 to 20, and the polyoxypropylene alkyl ether is 3 to 100.
　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としては、例えば、ポリオキシエチレン（９）ポリオキシプロピレン（１０）ブチルエーテル、ポリオキシエチレン（１７）ポリオキシプロピレン（１７）ブチルエーテル、ポリオキシエチレン（３０）ポリオキシプロピレン（３０）ブチルエーテル、ポリオキシエチレン（３７）ポリオキシプロピレン（３８）ブチルエーテル、ポリオキシエチレン（１０）ポリオキシプロピレン（８）セチルエーテル、ポリオキシエチレン（２０）ポリオキシプロピレン（８）セチルエーテル等が挙げられる。
　アルキル基の炭素数は１～３０が好ましく、より好ましくは１～５である。アルキル基の炭素数が前記範囲であると本発明の所望の効果が十分に得られ、害虫忌避組成物とする際に各種成分との相溶性が高く、さらに使用感が良いという効果を得ることができる。また、オキシエチレンの平均付加モル数は、５～１００が好ましく、より好ましくは５～５０である。オキシプロピレンの平均付加モル数は、５～１００が好ましく、より好ましくは５～５０である。オキシプロピレンの平均付加モル数が前記範囲であると、本発明の所望の効果を十分に得ることができる。 Examples of the polyoxyethylene polyoxypropylene alkyl ether include polyoxyethylene (9) polyoxypropylene (10) butyl ether, polyoxyethylene (17) polyoxypropylene (17) butyl ether, polyoxyethylene (30) polyoxypropylene (30) Butyl ether, polyoxyethylene (37) polyoxypropylene (38) butyl ether, polyoxyethylene (10) polyoxypropylene (8) cetyl ether, polyoxyethylene (20) polyoxypropylene (8) cetyl ether, etc. Can be mentioned.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 5 carbon atoms. When the carbon number of the alkyl group is within the above range, the desired effect of the present invention can be sufficiently obtained, and when it is used as a pest repellent composition, the compatibility with various components is high, and further the usability is good. Can do. Further, the average added mole number of oxyethylene is preferably 5 to 100, more preferably 5 to 50. The average added mole number of oxypropylene is preferably 5 to 100, more preferably 5 to 50. The desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
　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は、市販のものを使用することができ、例えば、日油株式会社製の「ユニルーブ５０ＭＢ－１１」、「ユニルーブ５０ＭＢ－２６」、「ユニルーブ５０ＭＢ－７２」、「ユニルーブ５０ＭＢ－１６８」、「ユニセーフ１０Ｐ」、「ユニセーフ２０Ｐ－８」（いずれも商品名）、三洋化成工業株式会社製の「ニューポール５０ＨＢ－５５」、「ニューポール５０ＨＢ－１００」、「ニューポール５０ＨＢ－２６０」、「ニューポール５０ＨＢ－４００」、「ニューポール５０ＨＢ－６６０」、「ニューポール５０ＨＢ－２０００」、「ニューポール５０ＨＢ－５１００」（いずれも商品名）等が挙げられる。 As the polyoxyethylene polyoxypropylene alkyl ether, commercially available products can be used. For example, “Unilube 50MB-11”, “Unilube 50MB-26”, “Unilube 50MB-72”, "UniLube 50MB-168", "Unisafe 10P", "Unisafe 20P-8" (all trade names), "New Pole 50HB-55", "New Pole 50HB-100", "New Pole" manufactured by Sanyo Chemical Industries, Ltd. 50HB-260 "," New Pole 50HB-400 "," New Pole 50HB-660 "," New Pole 50HB-2000 "," New Pole 50HB-5100 "(all trade names).
　ポリオキシプロピレンジグリセリルエーテルとしては、例えば、ポリオキシプロピレン（９）ジグリセリルエーテル、ポリオキシプロピレン（１４）ジグリセリルエーテル等が挙げられる。
　オキシプロピレンの平均付加モル数は、３～２０が好ましく、より好ましくは５～１５である。オキシプロピレンの平均付加モル数が前記範囲であると、本発明の所望の効果を十分に得ることができる。 Examples of the polyoxypropylene diglyceryl ether include polyoxypropylene (9) diglyceryl ether and polyoxypropylene (14) diglyceryl ether.
The average added mole number of oxypropylene is preferably from 3 to 20, more preferably from 5 to 15. The desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
　ポリオキシプロピレンジグリセリルエーテルは、市販のものを使用することができ、例えば、日油株式会社製の「ユニルーブＤＧＰ－７００」、「ユニルーブＤＧＰ－９５０」（いずれも商品名）、阪本薬品工業株式会社製の「ＳＹ－ＤＰ１４」、「ＳＹ－ＤＰ９」（いずれも商品名）等が挙げられる。 As the polyoxypropylene diglyceryl ether, commercially available products can be used. For example, “Unilube DGP-700”, “Unilube DGP-950” (both trade names) manufactured by NOF Corporation, Sakamoto Pharmaceutical Co., Ltd. Examples include “SY-DP14” and “SY-DP9” (both are trade names) manufactured by the company.
　ポリオキシプロピレンアルキルエーテルとしては、例えば、ポリオキシプロピレン（１２）ブチルエーテル、ポリオキシプロピレン（５２）ブチルエーテル、ポリオキシプロピレン（１５）ステアリルエーテル等が挙げられる。
　アルキル基の炭素数は１～３０が好ましく、より好ましくは１～５である。アルキル基の炭素数が前記範囲であると本発明の所望の効果が十分に得られ、害虫忌避組成物とする際に各種成分との相溶性が高く、さらに使用感が良いという効果を得ることができる。また、オキシプロピレンの平均付加モル数は、３～１００が好ましく、より好ましくは３～６０である。オキシプロピレンの平均付加モル数が前記範囲であると、本発明の所望の効果を十分に得ることができる。 Examples of the polyoxypropylene alkyl ether include polyoxypropylene (12) butyl ether, polyoxypropylene (52) butyl ether, polyoxypropylene (15) stearyl ether, and the like.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 5 carbon atoms. When the carbon number of the alkyl group is within the above range, the desired effect of the present invention can be sufficiently obtained, and when it is used as a pest repellent composition, the compatibility with various components is high, and further the usability is good. Can do. The average number of moles of oxypropylene added is preferably 3 to 100, more preferably 3 to 60. The desired effect of this invention can fully be acquired as the average addition mole number of oxypropylene is the said range.
　ポリオキシプロピレンアルキルエーテルは、市販のものを使用することができ、例えば、日油株式会社製の「ユニルーブＭＢ－７」、「ユニルーブＭＢ－７００」、「ユニルーブＭＳ-７０Ｋ」（いずれも商品名）、クローダジャパン株式会社製の「ＡＲＬＡＭＯＬ　ＰＳ１５Ｅ」（商品名）等が挙げられる。 As the polyoxypropylene alkyl ether, commercially available products can be used. For example, “Uniluve MB-7”, “Unilube MB-700”, “Unilube MS-70K” (all trade names) manufactured by NOF Corporation. ), “ARLAMOL PS15E” (trade name) manufactured by Croda Japan Co., Ltd., and the like.
　上記した特定エーテル系化合物は、１種を単独で用いてもよく、２種以上を組合せて用いることもできる。
　本発明において、害虫忌避組成物とする際に各種成分との相溶性の観点から、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としては、ポリオキシエチレン（９）ポリオキシプロピレン（１０）ブチルエーテル、ポリオキシエチレン（１７）ポリオキシプロピレン（１７）ブチルエーテル、ポリオキシエチレン（３０）ポリオキシプロピレン（３０）ブチルエーテル、ポリオキシエチレン（３７）ポリオキシプロピレン（３８）ブチルエーテルを用いることが好ましく、ポリオキシプロピレンジグリセリルエーテルとしては、ポリオキシプロピレン（９）ジグリセリルエーテルを用いることが好ましく、ポリオキシプロピレンアルキルエーテルとしては、ポリオキシプロピレン（１２）ブチルエーテル、ポリオキシプロピレン（５２）ブチルエーテルを用いることが好ましい。また、害虫忌避剤の皮膚内部への浸透抑制効果が高いという点から、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を用いることが好ましい。 The above-mentioned specific ether compounds may be used alone or in combination of two or more.
In the present invention, the polyoxyethylene polyoxypropylene alkyl ether includes polyoxyethylene (9) polyoxypropylene (10) butyl ether, polyoxyethylene, from the viewpoint of compatibility with various components when making a pest repellent composition. (17) Polyoxypropylene (17) butyl ether, polyoxyethylene (30) polyoxypropylene (30) butyl ether, polyoxyethylene (37) polyoxypropylene (38) butyl ether are preferably used, and polyoxypropylene diglyceryl ether As polyoxypropylene (9) diglyceryl ether, it is preferable to use polyoxypropylene (12) butyl ether, polyoxypropylene ( It is preferred to use 2) ether. Moreover, it is preferable to use polyoxyethylene polyoxypropylene alkyl ether from the point that the penetration inhibitory effect of the pest repellent into the skin is high.
　本発明の特定エーテル系化合物を害虫忌避剤とともに皮膚に適用するに際しては、害虫忌避剤１００質量部に対して特定エーテル系化合物を１～３００質量部となるように用いることが好ましく、より好ましくは３～２００質量部、更に好ましくは５～１００質量部である。害虫忌避剤１００質量部に対して特定エーテル系化合物を１質量部以上で用いることで害虫忌避剤の皮膚への浸透抑制効果を適切に得ることができ、３００質量部以下で用いることで害虫忌避剤の忌避効果を適切に得ることができ、本発明の所望の効果を十分に得ることができる。配合量が多すぎると、有効成分が揮散せずに効果的な忌避ができなくなる場合がある。 When the specific ether compound of the present invention is applied to the skin together with a pest repellent, it is preferable to use the specific ether compound in an amount of 1 to 300 parts by mass, more preferably 100 parts by mass of the pest repellent. The amount is 3 to 200 parts by mass, more preferably 5 to 100 parts by mass. By using the specific ether compound at 1 part by mass or more with respect to 100 parts by mass of the pest repellent, it is possible to appropriately obtain the effect of inhibiting penetration of the pest repellent into the skin, and by using it at 300 parts by mass or less The repellent effect of the agent can be appropriately obtained, and the desired effect of the present invention can be sufficiently obtained. When there are too many compounding quantities, an active ingredient may not volatilize and effective repelling may become impossible.
　本発明の特定エーテル系化合物を害虫忌避剤とともに皮膚に適用するに際しては、害虫忌避剤及び特定エーテル系化合物の両者を同時に適用してもよいし、別々に分けて適用してもよい。皮膚全体に塗り延ばしやすい点、ディートなどの害虫忌避剤の刺激が緩和される点、さらには簡便性の観点から、両者を含有する製剤として同時に皮膚に適用することが好ましい。 When applying the specific ether compound of the present invention to the skin together with the pest repellent, both the pest repellent and the specific ether compound may be applied simultaneously or separately. From the viewpoint of easy spreading on the entire skin, the stimulation of pest repellents such as diet, etc. being alleviated, and from the viewpoint of simplicity, it is preferable to apply both to the skin at the same time.
　害虫忌避剤及び特定エーテル系化合物を皮膚に適用するに際しては、例えば、ポンプ剤、ローション剤、ウェットティッシュ剤、ロールオン剤、塗布剤、ジェル剤、クリーム剤、エアゾール剤等の各種製剤として皮膚に適用することができる。 When applying pest repellents and specific ether compounds to the skin, for example, pumps, lotions, wet tissues, roll-on agents, coating agents, gels, creams, aerosols, etc. can do.
　これらの製剤とするには、本発明の効果を奏する限りにおいて、公知の溶剤、乳化・分散剤、噴射剤等を用いて調製し、さらに必要に応じて、不織布、塗布具、ポンプ装置、エアゾール装置等と組合せて所望の製剤形態とすればよい。 These preparations are prepared using known solvents, emulsifying / dispersing agents, propellants and the like as long as the effects of the present invention are obtained, and further, if necessary, nonwoven fabrics, applicators, pump devices, aerosols What is necessary is just to make it a desired formulation form combining with an apparatus etc.
　使用できる溶剤としては、例えば、水道水、精製水、イオン水等の水、エチルアルコール、イソプロピルアルコール、ラウリルアルコール、セタノール、２－ヘキシルデカノール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール、ラノリンアルコール等の低級アルコール、エチレングリコール、ジエチレングリコールモノエチルエーテル、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－ブチレングリコール、１，３－ペンタンジオール、グリセリン等の多価アルコール、炭化水素系溶剤等が挙げられる。 Solvents that can be used include, for example, tap water, purified water, ionic water, and the like, ethyl alcohol, isopropyl alcohol, lauryl alcohol, cetanol, 2-hexyldecanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, lanolin alcohol, and the like. Examples include alcohols, ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,3-pentanediol, glycerol and other polyhydric alcohols, hydrocarbon solvents, and the like. .
　また、乳化・分散剤としては、例えば、ソルビタントリオレート、ポリオキシエチレンモノオレート、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ノニルフェニルエーテル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルエーテル、デカグリセリンモノオレート、ジオレイン酸プロピレングリコール、ポリオキシエチレンステアリン酸アミド、ポリオキシエチレンラウリルエーテルリン酸、グリセリン脂肪酸エステル、ステアリルアルコール、ポリビニルピロリドン、ラノリン脂肪酸、トリイソステアリン酸ポリオキシエチレングリセリル等の界面活性剤、低級アルコール、多価アルコール等が挙げられる。 Examples of the emulsifying / dispersing agent include sorbitan trioleate, polyoxyethylene monooleate, polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, decaglycerin mono Surfactant such as oleate, propylene glycol dioleate, polyoxyethylene stearamide, polyoxyethylene lauryl ether phosphate, glycerin fatty acid ester, stearyl alcohol, polyvinyl pyrrolidone, lanolin fatty acid, polyisoethylene stearate polyoxyethylene glyceryl, lower alcohol And polyhydric alcohols.
　害虫忌避剤及び特定エーテル系化合物を皮膚上に適用するに際しては、例えば、害虫忌避剤がディートである場合、ディートの皮膚への付着量が１．５ｍｇ／１００ｃｍ２以上、さらに好ましくは５．０ｍｇ／１００ｃｍ２以上、かつ特定エーテル系化合物の皮膚への付着量が０．３ｍｇ／１００ｃｍ２以上となるように適用するのが好ましい。ディート及び特定エーテル系化合物の皮膚への付着量を前記範囲とすることで、害虫忌避効果及び皮膚への浸透抑制効果を十分に得ることができる。さらに、良好な使用感を得るという観点から、ディートは１．５～１５０ｍｇ／１００ｃｍ２、本発明の特定エーテル系化合物は０．３～４５０ｍｇ／１００ｃｍ２の付着量で用いることがより好ましい。 When applying the pest repellent and the specific ether compound on the skin, for example, when the pest repellent is a diet, the adherence amount of the diet to the skin is 1.5 mg / 100 cm 2 or more, more preferably 5.0 mg. / 100 cm 2 or more, and the specific ether compound is preferably applied so that the amount of the specific ether compound attached to the skin is 0.3 mg / 100 cm 2 or more. By making the adhesion amount of the diet and the specific ether compound to the skin within the above range, a pest repellent effect and a skin penetration inhibiting effect can be sufficiently obtained. Further, from the viewpoint of obtaining a good feeling in use, it is more preferable to use a diet with an amount of 1.5 to 150 mg / 100 cm 2 and the specific ether compound of the present invention with an amount of 0.3 to 450 mg / 100 cm 2 .
　この好ましい条件を得るためには、例えば、皮膚に適用する際にエアゾール剤やポンプ剤を使用する場合には、噴口、バルブ、噴射圧などを調整したり、塗布剤、ロールオン剤やウェットティッシュ剤を使用する場合においては、塗布面形状や塗布部の材質性状などを調整するなどして、皮膚への害虫忌避剤及び特定エーテル系化合物の付着量を調整すればよい。 In order to obtain this preferable condition, for example, when an aerosol agent or a pump agent is used when applied to the skin, a nozzle, a valve, an injection pressure, etc. are adjusted, a coating agent, a roll-on agent or a wet tissue agent. In the case of using, the adhesion amount of the pest repellent and the specific ether compound to the skin may be adjusted by adjusting the shape of the coated surface or the material property of the coated part.
　前記製剤をエアゾール剤として皮膚に適用するには、製剤全体に対して噴射剤が４０～９５ｖ／ｖ％となるようにエアゾール容器に加圧充填すればよい。噴射剤としては、例えば、液化石油ガス、ジメチルエーテル、代替フロン、圧縮ガス（二酸化炭素、窒素）、及びこれらの混合物等を用いることができる。 In order to apply the preparation to the skin as an aerosol, the aerosol container may be pressurized and filled so that the propellant is 40 to 95 v / v% with respect to the whole preparation. As the propellant, for example, liquefied petroleum gas, dimethyl ether, alternative chlorofluorocarbon, compressed gas (carbon dioxide, nitrogen), and a mixture thereof can be used.
　また前記製剤をウェットティッシュ剤として皮膚に適用するには、支持体の目付量が２０～８０ｇ／ｍ２であることが好ましい。支持体の目付量が２０～８０ｇ／ｍ２であることによって所望の害虫忌避剤及び特定エーテル系化合物の取り込み、保持、塗布、含浸が可能になる。 In order to apply the preparation to the skin as a wet tissue agent, the basis weight of the support is preferably 20 to 80 g / m 2 . When the basis weight of the support is 20 to 80 g / m 2, it is possible to incorporate, hold, apply and impregnate a desired pest repellent and a specific ether compound.
　また、厚さが０．１～５ｍｍ程度の支持体に、害虫忌避剤を７０～３００ｍｌ／ｍ２保持させることが好ましい。害虫忌避剤を支持体に７０～３００ｍｌ／ｍ２保持させることによって、所望の害虫忌避剤及び本発明のエーテル系化合物の取り込み、保持、塗布、含浸が可能になる。 Further, it is preferable to hold the pest repellent at 70 to 300 ml / m 2 on a support having a thickness of about 0.1 to 5 mm. By holding the pest repellent on the support at 70 to 300 ml / m 2 , it is possible to incorporate, hold, apply and impregnate the desired pest repellent and the ether compound of the present invention.
　支持体としては、ネル、綿、絹、ポリエステル、ナイロン、これらを素材としたもの等の織布；ポリエステル、ポリオレフィン、ナイロン、綿、レーヨン、ビニロン、セルロース、これらを素材としたもの等の不織布；ポリエチレン、ポリプロピレン、エチレン－酢酸ビニル共重合体、ポリ塩化ビニル等を発泡させたシート状の樹脂発泡体等を用いることができる。 As a support, woven fabric such as flannel, cotton, silk, polyester, nylon, or the like made from these materials; non-woven fabric such as polyester, polyolefin, nylon, cotton, rayon, vinylon, cellulose, or the like made from these materials; A sheet-like resin foam obtained by foaming polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like can be used.
　各種製剤には、使用感を向上させたり、害虫忌避効果を高めたり、殺菌効果を付与する等を目的として、例えば、任意の量の粉体、香料成分、殺菌・防腐成分、保湿成分、増粘剤、滑沢剤、可溶剤、ｐＨ調整剤、安定剤等を含有することができる。 For various preparations, for example, an arbitrary amount of powder, a fragrance component, a sterilizing / preserving component, a moisturizing component, an increasing amount, for the purpose of improving the feeling of use, increasing the repellent effect of pests, or imparting a bactericidal effect. A viscosity agent, a lubricant, a solubilizer, a pH adjuster, a stabilizer and the like can be contained.
　例えば、疎水性シリカ、ケイ酸カルシウム、ケイソウ土、高純度シリカ、無水ケイ酸、タルク、炭酸カルシウム、ステアリン酸マグネシウム、酸性白土、ホワイトカーボン、パーライト等の無機粉体；オクテニルコハク酸トウモロコシデンプンエステルアルミニウム等のアルケニルコハク酸デンプンの金属塩；シルクパウダー等の天然パウダー；ナイロン、ポリプロピレン等の樹脂等の粉体；メントール、ハッカオイル、ミントオイル等の香料成分；フェノール、パラオキシ安息香酸エステル、サリチル酸及びその塩、塩化ベンザルコニウム、塩化セチルピリジニウム、グルコン酸クロルヘキシジン、フェノキシエタノール等の殺菌・防腐成分；ヒアルロン酸ナトリウム、セラミド、コラーゲン、プラセンタエキス、ミルクプロテイン、ソルビット、グリセリン、アスコルビン酸（ビタミンＣ誘導体）、Ｎ－ステアロイルフィトスフィンゴジン、グリチルリチン酸ジカリウム、メドウフォーム油、天然ビタミンＥ等の保湿成分（湿潤剤）；カルボキシビニルポリマー、３－オクタデシルオキシ－２－ヒドロキシプロピル２－ヒドロキシプロピルメチルセルロース、アクリル酸・メタクリル酸アルキル共重合体等の増粘剤；パラアミノ安息香酸エステル、シノキサート、オキシベンゼン等の紫外線吸収・遮断成分；クロルヒドロキシアルミニウム、アルミニウム・ジルコニウムクロルヒドレート等の制汗・消臭成分；ベニバナ等の色素成分；オクタメチルトリシロキサン、デカメチルテトラシロキサン、メチルポリシロキサン、ポリオキシエチレン・メチルポリシロキサン共重合体等の滑沢剤；クエン酸、クエン酸ナトリウム、アルギニン、トリイソプロパノールアミン等のｐＨ調整剤；グリセリンモノ２－エチルヘキシルエーテル、ジエチレントリアミン五酢酸五ナトリウム液等の安定剤等が挙げられる。 For example, inorganic powder such as hydrophobic silica, calcium silicate, diatomaceous earth, high purity silica, anhydrous silicic acid, talc, calcium carbonate, magnesium stearate, acid clay, white carbon, pearlite; octenyl succinic acid corn starch ester aluminum, etc. Metal salts of alkenyl succinate starch; natural powders such as silk powder; powders such as resins such as nylon and polypropylene; fragrance ingredients such as menthol, mint oil, mint oil; phenol, paraoxybenzoic acid ester, salicylic acid and salts thereof Bactericidal and antiseptic ingredients such as benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, phenoxyethanol; sodium hyaluronate, ceramide, collagen, placenta extract, milk protein, soy Moisturizing ingredients (wetting agents) such as bit, glycerin, ascorbic acid (vitamin C derivative), N-stearoyl phytosphingodine, dipotassium glycyrrhizinate, meadowfoam oil, natural vitamin E; carboxyvinyl polymer, 3-octadecyloxy-2- Thickeners such as hydroxypropyl 2-hydroxypropylmethylcellulose, acrylic acid / alkyl methacrylate copolymer; UV-absorbing / blocking components such as paraaminobenzoic acid ester, synoxate, oxybenzene; chlorohydroxyaluminum, aluminum / zirconium chlorohydrate Antiperspirant / deodorant components such as safflower, etc. Pigment components such as safflower; octamethyltrisiloxane, decamethyltetrasiloxane, methylpolysiloxane, polyoxyethylene / methylpolysiloxane copolymer Lubricants; citric acid, sodium citrate, arginine, pH adjusting agents such as triisopropanolamine; glycerin mono-2-ethylhexyl ether, stabilizing agents such as diethylenetriaminepentaacetic acid pentasodium solution and the like.
　さらにミリスチン酸イソプロピル、ラウリン酸ヘキシル等の高級脂肪酸エステル；アロエ、モモ、トウキ、冬虫夏草、トマト、ニンジン、ブクリョウ、アカブドウ、アシタバ、アルテア、アルニカ、カイソウ、キューカンバ、紅茶、ゴボウ、シイタケ、ジオウ、タイソウ、甜茶、プハーン、ヘチマ、ボタン、ユリ、リンゴ、レイシ等の植物抽出物；シリコーン等を配合することにより、害虫忌避効果の持続と使用感の更なる向上を図ることができる。 In addition, higher fatty acid esters such as isopropyl myristate and hexyl laurate; aloe, peach, touki, cordyceps, tomato, carrot, boucle, red grape, ashitaba, artea, arnica, diatom, cucumber, tea, burdock, shiitake, jiou, taiso, By blending plant extracts such as strawberry tea, phan, loofah, button, lily, apple, litchi; silicone, etc., the pest repellent effect can be maintained and the feeling of use can be further improved.
　本発明において忌避の対象となりうる害虫としては、例えば、カ、ブユ、イエダニ、ノミ、サシバエ、ナンキンムシ、ヤマビル、マダニ、ハチ、アリ、アブ、ツツガムシ等の各種の刺咬性害虫が挙げられる。 Examples of the pests that can be repelled in the present invention include various biting pests such as mosquitoes, flyfish, house dust mites, fleas, sand flies, bed bugs, mountain bills, ticks, bees, ants, abs, and tsutsugamushi.
　本発明は、害虫忌避剤の皮膚内部への浸透を抑えるため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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用するという、前記特定エーテル系化合物の用途に関するものであり、本発明を適用することで、害虫忌避効果の持続性が向上し、かつ皮膚に対する刺激が抑制された害虫忌避組成物が提供される。 The present invention relates to at least one ether system selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether in order to suppress penetration of the pest repellent into the skin. The compound is applied to the skin together with a pest repellent, and relates to the use of the specific ether compound. By applying the present invention, the persistence of the pest repellent effect is improved and the irritation to the skin is suppressed. A pest repellent composition is provided.
　害虫忌避剤としては、前述したような各種化合物が挙げられる。害虫忌避剤の含有量は、害虫忌避組成物に対して、通常、０．１～９９．５ｗ／ｖ％、より好ましくは０．１～５０ｗ／ｖ％、さらに好ましくは０．５～５０ｗ／ｖ％、特に好ましくは１～３０ｗ／ｖ％である。害虫忌避剤の含有量が１ｗ／ｖ％以上であると、持続効果が顕著であるため好ましく、３０ｗ／ｖ％以下であると、べたつきが少ないため好ましい。 Examples of the insect repellent include various compounds as described above. The content of the pest repellent is usually 0.1 to 99.5 w / v%, more preferably 0.1 to 50 w / v%, still more preferably 0.5 to 50 w / v based on the pest repellent composition. It is v%, particularly preferably 1 to 30 w / v%. When the content of the pest repellent is 1 w / v% or more, the sustained effect is remarkable, and when it is 30 w / v% or less, the stickiness is small.
　皮膚における害虫忌避効果の持続性を向上させる効果を得るためには、有効量の特定エーテル系化合物を皮膚上に適用する必要がある。特定エーテル系化合物の有効量として好ましくは、害虫忌避組成物に対して０．１～９９．５ｗ／ｖ％、より好ましくは０．１～５０ｗ／ｖ％、さらに好ましくは０．５～３０ｗ／ｖ％、特に好ましくは０．５～１０ｗ／ｖ％である。特定エーテル系化合物の含有量が０．５ｗ／ｖ％以上であると、持続効果が顕著であるため好ましく、１０ｗ／ｖ％以下であると、べたつきが少ないため好ましい。 In order to obtain the effect of improving the sustainability of the pest repellent effect on the skin, it is necessary to apply an effective amount of the specific ether compound on the skin. The effective amount of the specific ether compound is preferably 0.1 to 99.5 w / v%, more preferably 0.1 to 50 w / v%, still more preferably 0.5 to 30 w / v with respect to the pest repellent composition. It is v%, particularly preferably 0.5 to 10 w / v%. When the content of the specific ether compound is 0.5 w / v% or more, the sustained effect is remarkable, and when it is 10 w / v% or less, the stickiness is small.
　上記害虫忌避組成物においては、害虫忌避剤の含有量を１００質量部としたときの特定エーテル系化合物の含有量が１～３００質量部であることが好ましく、５～１００質量部であることがより好ましい。上記範囲であることで、特定エーテル系化合物の害虫忌避剤の皮膚への浸透を抑制する効果がより高くなる。 In the above-mentioned pest repellent composition, the content of the specific ether compound is preferably 1 to 300 parts by mass when the content of the pest repellent is 100 parts by mass, and preferably 5 to 100 parts by mass. More preferred. By being the said range, the effect which suppresses the penetration | invasion to the skin of the pest repellent of a specific ether type compound becomes higher.
　上記害虫忌避組成物は、前述したような、ポンプ剤、ローション剤、ウェットティッシュ剤、ロールオン剤、塗布剤、ジェル剤、クリーム剤、エアゾール剤等の各種製剤として用いることができる。 The pest repellent composition can be used as various preparations such as a pump agent, a lotion agent, a wet tissue agent, a roll-on agent, a coating agent, a gel agent, a cream agent and an aerosol agent as described above.
　これらの製剤とするには、本発明の効果が奏する限りにおいて、前述したような、公知の溶剤、乳化・分散剤、噴射剤等を用いて調製し、さらに必要に応じて、不織布、アクチュエーター、塗布具、ポンプ装置、エアゾール装置等と組合せて所期の製剤形態とすればよい。 In order to obtain these preparations, as long as the effects of the present invention are exhibited, the preparation is performed using a known solvent, an emulsifying / dispersing agent, a propellant, etc. as described above, and if necessary, a nonwoven fabric, an actuator, What is necessary is just to combine with an applicator, a pump apparatus, an aerosol apparatus, etc., and to make it a desired formulation form.
　本発明はまた、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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物からなる、害虫忌避剤の皮膚への浸透抑制剤を提供するものである。この浸透抑制剤は、本発明の特定エーテル系化合物を含有しているため、害虫忌避剤の皮膚内部への浸透を抑え、害虫忌避剤をより長時間表皮に滞留させることができる。 The present invention also relates to penetration of a pest repellent into the skin, comprising at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether. An inhibitor is provided. Since this penetration inhibitor contains the specific ether compound of the present invention, the penetration of the pest repellent into the skin can be suppressed, and the pest repellent can be retained in the epidermis for a longer time.
　以下、実施例および比較例により本発明をさらに説明するが、本発明は下記例に何ら制限されるものではない。 Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.
＜試験例１：皮膚吸収抑制試験＞
（実施例１～７、比較例１～３、参考例１）
　表１に示す処方に従い、各成分を撹拌下で混合して、害虫忌避組成物を調製した。
　得られた害虫忌避組成物を用いて下記試験方法に従い、ディート（ｌｏｇＰ：２）の皮膚への残存量を測定した。 <Test Example 1: Skin absorption inhibition test>
(Examples 1 to 7, Comparative Examples 1 to 3, Reference Example 1)
According to the formulation shown in Table 1, each component was mixed with stirring to prepare a pest repellent composition.
Using the obtained pest repellent composition, the amount of diet (log P: 2) remaining on the skin was measured according to the following test method.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔試験方法〕
　試験装置として、図１に示す水平型拡散セル（ビードレックス社製、平板膜用水平型パームセル）を使用した。水平型拡散セル１０はウォータージャケット４に覆われたレセプターセル２とドナーセル１１が試料膜（皮膚１）を介して水平状態で対設された装置であり、レセプターセル２とドナーセル１１は互いに接合及び離隔可能である。本試験において、ドナーセル１１側は試料膜の固定のために用いている。 〔Test method〕
As a test apparatus, the horizontal diffusion cell (made by Beadrex, horizontal palm cell for flat membrane) shown in FIG. 1 was used. The horizontal diffusion cell 10 is a device in which a receptor cell 2 and a donor cell 11 covered with a water jacket 4 are arranged in a horizontal state through a sample film (skin 1), and the receptor cell 2 and the donor cell 11 are joined to each other. Can be separated. In this test, the donor cell 11 side is used for fixing the sample film.
１．マウスの皮膚１（ラボスキン、株式会社星野実験動物飼育所より入手）を水平型拡散セル１０に、皮膚１の真皮側がレセプターセル２側に位置するように取り付けた。
２．皮膚１の角層側（４．９ｃｍ２）に、上記調製した害虫忌避組成物を約４５μＬ処理し、アルミ箔８で覆い、締め付けノブ６で皮膚１を固定した。
３．レセプターセル２に生理食塩水９を５０ｍＬを充填し、セルを生理食塩水９で満たした。
４．試験の間、レセプターセル２はスターラー３でセル内の生理食塩水を撹拌させ、レセプターセル２を覆っているウォータージャケット４には、ヒーター／サーキュレーター５により、３７℃の温水を循環させることで、レセプターセル２内の温度を３７℃で一定に保った。
５．レセプターセル２内の温度が３７℃になった時点から、１時間毎にレセプターセル２のサンプリング・ポート７より生理食塩水９を３ｍＬサンプリングした。その後同量の生理食塩水をレセプターセル２に戻し、液量を一定にした。
６．サンプリング液中のディート量を高速液体クロマトグラフィー（ＨＰＬＣ）によって測定した。
　ＨＰＬＣ測定条件
　　使用カラム：ＳＴＲ　ＯＤＳ－ＩＩ（株式会社島津ジーエルシー製、２５０Ｌ×４．６ｍｍ　Ｉ．Ｄ．）
　　検出器：紫外線吸光検出器
　　波長　：２５４ｍｍ
　　移動相：アセトニトリル／水＝６０／４０
　　流速　：１ｍＬ／ｍｉｎ
　　カラム温度：４０℃
７．下記式により、皮膚上残存量を算出した。なお、皮膚上残存量（ｍｇ／ｃｍ２）は小数第三位を四捨五入した数値とした。
　ディートの皮膚上残存量（ｍｇ／ｃｍ２）＝（処理ディート量－サンプリングした液中のディート量×５０／３）／処理面積 1. Mouse skin 1 (lab skin, obtained from Hoshino Experimental Animal Breeding Co., Ltd.) was attached to the horizontal diffusion cell 10 so that the dermis side of the skin 1 was positioned on the receptor cell 2 side.
2. About 45 μL of the prepared insect repellent composition was treated on the horny layer side (4.9 cm 2 ) of the skin 1, covered with aluminum foil 8, and the skin 1 was fixed with the tightening knob 6.
3. Receptor cell 2 was filled with 50 mL of physiological saline 9 and the cell was filled with physiological saline 9.
4). During the test, the receptor cell 2 stirs the physiological saline in the cell with a stirrer 3, and hot water at 37 ° C. is circulated through the heater / circulator 5 to the water jacket 4 covering the receptor cell 2. The temperature in the receptor cell 2 was kept constant at 37 ° C.
5). From the time when the temperature in the receptor cell 2 reached 37 ° C., 3 mL of physiological saline 9 was sampled from the sampling port 7 of the receptor cell 2 every hour. Thereafter, the same amount of physiological saline was returned to the receptor cell 2 to keep the liquid volume constant.
6). The amount of diet in the sampling solution was measured by high performance liquid chromatography (HPLC).
HPLC measurement conditions Column used: STR ODS-II (manufactured by Shimadzu GL Corporation, 250 L × 4.6 mm ID)
Detector: UV absorption detector Wavelength: 254mm
Mobile phase: acetonitrile / water = 60/40
Flow rate: 1 mL / min
Column temperature: 40 ° C
7). The residual amount on the skin was calculated by the following formula. The residual amount on the skin (mg / cm 2 ) was a value obtained by rounding off the third decimal place.
Amount of diet remaining on skin (mg / cm 2 ) = (Amount of treated diet−Amount of diet in sampled liquid × 50/3) / Area treated
　上記試験により得られた結果を表２に示す。なお、皮膚上残存量が０．０５ｍｇ／ｃｍ２以上であれば、忌避効果を有すると判断できる。 Table 2 shows the results obtained by the above test. If the residual amount on the skin is 0.05 mg / cm 2 or more, it can be determined that it has a repellent effect.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から、比較例１～３は測定開始から３時間後には皮膚上におけるディートの残存量が０．０４ｍｇ／ｃｍ２以下となり、忌避効果の有効量を３時間以上、皮膚上に残存させることができなかった。これに対し、実施例１～７は、測定開始から３時間後においてもディートの残存量が０．０５ｍｇ／ｃｍ２以上であり、忌避効果の有効量を３時間以上、皮膚上に残存させることができた。特に、実施例１～４、６、７は測定開始から３時間後のディートの残存量が０．１０ｍｇ／ｃｍ２以上であり、中でも実施例１～３、６は測定開始から４時間後においてもディートの残存量が０．０５ｍｇ／ｃｍ２以上であった。
　これらの結果より、実施例１～７は、害虫忌避剤の皮膚内部への浸透を抑え、皮膚上に長期間に亘り滞留させることができることがわかった。 From the results of Table 2, in Comparative Examples 1 to 3, the residual amount of diet on the skin was 0.04 mg / cm 2 or less after 3 hours from the start of measurement, and the effective amount of the repellent effect remained on the skin for 3 hours or more. I couldn't let you. On the other hand, in Examples 1 to 7, the residual amount of diet is 0.05 mg / cm 2 or more even after 3 hours from the start of measurement, and the effective amount of the repellent effect is allowed to remain on the skin for 3 hours or more. I was able to. Particularly, in Examples 1 to 4, 6, and 7, the residual amount of diet after 3 hours from the start of measurement is 0.10 mg / cm 2 or more, and in particular, Examples 1 to 3, and 6 are 4 hours after the start of measurement. The residual amount of diet was 0.05 mg / cm 2 or more.
From these results, it was found that Examples 1 to 7 can suppress the penetration of the pest repellent into the skin and can stay on the skin for a long time.
＜試験例２：吸血阻止試験＞
（実施例８～９、比較例４～５）
　表３に示す処方に従い、各成分を撹拌下で混合して、害虫忌避組成物を調製した。
　得られた害虫忌避組成物を用いて下記試験方法に従い、忌避率を測定した。 <Test Example 2: Blood absorption prevention test>
(Examples 8 to 9, Comparative Examples 4 to 5)
According to the formulation shown in Table 3, each component was mixed under stirring to prepare a pest repellent composition.
Using the obtained pest repellent composition, the repellent rate was measured according to the following test method.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
〔試験方法〕
　以下の手順により試験を行った。
１．開閉可能な腕挿入窓（約１１３ｃｍ２）を備えた金属ケージ（縦２５ｃｍ×横２５ｃｍ×高さ２５ｃｍ）に雌ヒトスジシマカ約５０頭を放した。
２．上記調製した害虫忌避組成物を、被験者の手の甲に塗布し、塗布後、手の甲の部分を５ｃｍ×５ｃｍの略正方形状に切り取ったゴム手袋を着用した。塗布量は１．３４μＬ／ｃｍ２であった。
３．ゴム手袋の着用後、１時間毎に、ヒトスジシマカが放たれた金属ケージの腕挿入窓から手を入れ、その状態を３００秒間保ち、手の甲の露出部分（５ｃｍ×５ｃｍ）へのヒトスジシマカのランディング数をカウントした。各例につき３回又は４回行い、その平均値を算出した。
４．無処理区として、被験者の他方の手について、害虫忌避組成物を塗布せずに同様の試験を行った。手の甲の部分を５ｃｍ×５ｃｍの略正方形状に切り取ったゴム手袋を着用し、着用後１時間毎のヒトスジシマカのランディング数をカウントした。各例につき３回又は４回行い、その平均値を算出した。
５．害虫忌避組成物を処理した場合（処理区）のヒトスジシマカのランディング数と無処理区のヒトスジシマカのランディング数から、下記式により、忌避率を算出した。
　忌避率（％）＝（無処理区ランディング数－処理区ランディング数）／無処理区ランディング数×１００ 〔Test method〕
The test was conducted according to the following procedure.
1. About 50 female Aedes albopictus were released in a metal cage (length 25 cm × width 25 cm × height 25 cm) equipped with an openable and closable arm insertion window (about 113 cm 2 ).
2. The prepared pest repellent composition was applied to the back of the subject's hand, and after application, a rubber glove with the back of the hand cut into a substantially square shape of 5 cm × 5 cm was worn. The coating amount was 1.34 μL / cm 2 .
3. Every hour after wearing rubber gloves, put your hand through the arm insertion window of the metal cage where the Aedes albopictus was released, keep that state for 300 seconds, and set the number of Aedes albopictus landing on the exposed part of the back of the hand (5 cm x 5 cm) I counted. Each example was performed 3 or 4 times, and the average value was calculated.
4). As an untreated section, the same test was conducted on the other hand of the subject without applying the pest repellent composition. Rubber gloves with the back of the hand cut into a substantially square shape of 5 cm × 5 cm were worn, and the number of landings of H. aedes albopictus every hour after wearing was counted. Each example was performed 3 or 4 times, and the average value was calculated.
5). The repellent rate was calculated by the following formula from the number of landings of Aedes albopictus in the case of treating the pest repellent composition (treated group) and the number of Aedes albopictus in the untreated group.
Repellent rate (%) = (No treatment area landing number-Treatment area landing number) / No treatment area landing number x 100
　上記試験により得られた結果を表４及び図２に示す。 The results obtained by the above test are shown in Table 4 and FIG.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４及び図２の結果から、ディートのみを含有した比較例５は忌避率８０％以上を示す継続時間は３時間であった。これに対し、比較例４は忌避率８０％以上が４時間継続されたが、実施例８、９は忌避率８０％以上を５時間以上継続することができることがわかった。 From the results of Table 4 and FIG. 2, in Comparative Example 5 containing only diet, the duration of the repelling rate of 80% or more was 3 hours. On the other hand, in Comparative Example 4, the repelling rate of 80% or more was continued for 4 hours, but in Examples 8 and 9, it was found that the repelling rate of 80% or more could be continued for 5 hours or more.
＜試験例３：吸血阻止試験＞
（実施例１０、比較例６～７）
　表５に示す処方に従い、各成分を撹拌下で混合して、害虫忌避組成物を調製した。なお、比較例６は試験例２の比較例５と同様の処方である。
　得られた害虫忌避組成物を用いて下記試験方法に従い、忌避率を測定した。 <Test Example 3: Blood absorption prevention test>
(Example 10, Comparative Examples 6-7)
According to the formulation shown in Table 5, each component was mixed with stirring to prepare a pest repellent composition. Comparative Example 6 has the same formulation as Comparative Example 5 in Test Example 2.
Using the obtained pest repellent composition, the repellent rate was measured according to the following test method.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
〔試験方法〕
　以下の手順により試験を行った。
１．開閉可能な腕挿入窓（約１１３ｃｍ２）を備えた金属ケージ（縦２５ｃｍ×横２５ｃｍ×高さ２５ｃｍ）に雌ヒトスジシマカ約５０頭を放した。
２．上記調製した害虫忌避組成物を、被験者の手の甲に塗布し、塗布後、手の甲の部分を５ｃｍ×５ｃｍの略正方形状に切り取ったゴム手袋を着用した。塗布量は０．８０μＬ／ｃｍ２であった。
３．ゴム手袋の着用後、１時間毎に、ヒトスジシマカが放たれたクリアケージの腕挿入窓から手を入れ、その状態を３００秒間保ち、手の甲の露出部分（５ｃｍ×５ｃｍ）へのヒトスジシマカのランディング数をカウントした。各例につき３回又は４回行い、その平均値を算出した。
４．無処理区として、被験者の他方の手について、害虫忌避組成物を塗布せずに同様の試験を行った。手の甲の部分を５ｃｍ×５ｃｍの略正方形状に切り取ったゴム手袋を着用し、着用後１時間毎のヒトスジシマカのランディング数をカウントした。各例につき３回又は４回行い、その平均値を算出した。
５．害虫忌避組成物を処理した場合（処理区）のヒトスジシマカのランディング数と無処理区のヒトスジシマカのランディング数から、下記式により、忌避率を算出した。
　忌避率（％）＝（無処理区ランディング数－処理区ランディング数）／無処理区ランディング数×１００ 〔Test method〕
The test was conducted according to the following procedure.
1. About 50 female Aedes albopictus were released in a metal cage (length 25 cm × width 25 cm × height 25 cm) equipped with an openable and closable arm insertion window (about 113 cm 2 ).
2. The prepared pest repellent composition was applied to the back of the subject's hand, and after application, a rubber glove with the back of the hand cut into a substantially square shape of 5 cm × 5 cm was worn. The coating amount was 0.80 μL / cm 2 .
3. Every hour after wearing rubber gloves, put your hand through the arm insertion window of the clear cage where the Aedes albopictus was released, keep that state for 300 seconds, and set the number of Aedes albopictus landing on the exposed part of the back of the hand (5 cm x 5 cm) I counted. Each example was performed 3 or 4 times, and the average value was calculated.
4). As an untreated section, the same test was conducted on the other hand of the subject without applying the pest repellent composition. Rubber gloves with the back of the hand cut into a substantially square shape of 5 cm × 5 cm were worn, and the number of landings of H. aedes albopictus every hour after wearing was counted. Each example was performed 3 or 4 times, and the average value was calculated.
5). The repellent rate was calculated by the following formula from the number of landings of Aedes albopictus in the case of treating the pest repellent composition (treated group) and the number of Aedes albopictus in the untreated group.
Repellent rate (%) = (No treatment area landing number-Treatment area landing number) / No treatment area landing number x 100
　上記試験により得られた結果を表６及び図３に示す。 The results obtained by the above test are shown in Table 6 and FIG.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表６及び図３の結果から、実施例１０は忌避率が８０％以上を示す継続時間が９時間であり、ディートの含有量が同じである比較例６よりも７時間、忌避率８０％以上を継続することができた。また、実施例１０は忌避率が８０％以上を示す継続時間が、ディートの含有量が３倍である比較例７と同等以上であった。
　この結果より、本発明によれば、害虫忌避剤を低濃度で用いても害虫忌避効果を長時間持続させることができることがわかった。 From the results of Table 6 and FIG. 3, Example 10 has a duration of 9 hours for which the repelling rate is 80% or more, 7 hours than Comparative Example 6 having the same diet content, and a repelling rate of 80% or more. Was able to continue. Further, in Example 10, the duration time in which the repelling rate was 80% or more was equal to or more than that in Comparative Example 7 in which the diet content was tripled.
From these results, it was found that according to the present invention, the pest repellent effect can be maintained for a long time even when the pest repellent is used at a low concentration.
　続いて、本発明に係る害虫忌避剤の皮膚への浸透抑制剤である特定エーテル系化合物を配合した製剤の処方例を以下に示す。 Subsequently, a formulation example of a formulation in which a specific ether compound that is a skin penetration inhibitor of the pest repellent according to the present invention is shown is shown below.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１６年８月１０日出願の日本特許出願（特願２０１６－１５８００７）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on August 10, 2016 (Japanese Patent Application No. 2016-158007), the contents of which are incorporated herein by reference.
１　　皮膚
２　　レセプターセル
３　　スターラー
４　　ウォータージャケット
５　　ヒーター／サーキュレーター
６　　締め付けノブ
７　　サンプリング・ポート
８　　アルミ箔
９　　生理食塩水
１０　水平型拡散セル
１１　ドナーセル DESCRIPTION OF SYMBOLS 1 Skin 2 Receptor cell 3 Stirrer 4 Water jacket 5 Heater / circulator 6 Tightening knob 7 Sampling port 8 Aluminum foil 9 Saline 10 Horizontal diffusion cell 11 Donor cell

Claims (9)

  1. 　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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用する害虫忌避剤の皮膚への浸透を抑制する方法。 Applying at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether to the skin together with the pest repellent to the skin A method to suppress penetration.
  2. 　前記害虫忌避剤が、Ｎ，Ｎ－ジエチル－ｍ－トルアミド、３－（Ｎ－ｎ－ブチル－Ｎ－アセチル）アミノプロピオン酸エチルエステル及び１－ピペリジンカルボン酸２－（２－ヒドロキシエチル）－１－メチルプロピルエステルからなる群から選択される少なくとも１つである、請求項１に記載の害虫忌避剤の皮膚への浸透を抑制する方法。 The pest repellent is N, N-diethyl-m-toluamide, 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1 The method for suppressing penetration of a pest repellent into skin according to claim 1, which is at least one selected from the group consisting of methylpropyl ester.
  3. 　前記エーテル系化合物のオキシプロピレンの平均付加モル数が、３～１００である、請求項１又は２に記載の害虫忌避剤の皮膚への浸透を抑制する方法。 The method for suppressing penetration of a pest repellent into skin according to claim 1 or 2, wherein the average addition mole number of oxypropylene of the ether compound is 3 to 100.
  4. 　前記害虫忌避剤１００質量部に対して、前記エーテル系化合物を１～３００質量部の範囲で使用する、請求項１～３のいずれか１項に記載の害虫忌避剤の皮膚への浸透を抑制する方法。 The pest repellent according to any one of claims 1 to 3, wherein the pest repellent is used in an amount of 1 to 300 parts by mass with respect to 100 parts by mass of the pest repellent. how to.
  5. 　前記害虫忌避剤が、Ｎ，Ｎ－ジエチル－ｍ－トルアミドであり、前記Ｎ，Ｎ－ジエチル－ｍ－トルアミドを１．５ｍｇ／１００ｃｍ２以上かつ前記エーテル系化合物を０．３ｍｇ／１００ｃｍ２以上となる付着量で用いる、請求項１～４のいずれか１項に記載の害虫忌避剤の皮膚への浸透を抑制する方法。 The pest repellent is N, N-diethyl-m-toluamide, the N, N-diethyl-m-toluamide is 1.5 mg / 100 cm 2 or more and the ether compound is 0.3 mg / 100 cm 2 or more. The method for suppressing penetration of a pest repellent according to any one of claims 1 to 4 into the skin, which is used at an adhesion amount of
  6. 　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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物からなる害虫忌避剤の皮膚への浸透抑制剤。 An insect pest repellent inhibitor comprising at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether.
  7. 　Ｎ，Ｎ－ジエチル－ｍ－トルアミド、３－（Ｎ－ｎ－ブチル－Ｎ－アセチル）アミノプロピオン酸エチルエステル及び１－ピペリジンカルボン酸２－（２－ヒドロキシエチル）－１－メチルプロピルエステルからなる群から選択される少なくとも１つの害虫忌避剤の皮膚への浸透を抑制するために用いられる、請求項６に記載の害虫忌避剤の皮膚への浸透抑制剤。 Consists of N, N-diethyl-m-toluamide, 3- (Nn-butyl-N-acetyl) aminopropionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester The penetration inhibitor for skin penetration of the pest repellent according to claim 6, which is used for suppressing penetration of at least one pest repellent selected from the group into the skin.
  8. 　オキシプロピレンの平均付加モル数が３～１００である、請求項６又は７に記載の害虫忌避剤の皮膚への浸透抑制剤。 The pest repellent penetration inhibitor for skin according to claim 6 or 7, wherein the average added mole number of oxypropylene is 3 to 100.
  9. 　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、ポリオキシプロピレンジグリセリルエーテル及びポリオキシプロピレンアルキルエーテルからなる群から選択される少なくとも１つのエーテル系化合物を害虫忌避剤とともに皮膚に適用する害虫忌避剤の皮膚に対する刺激を抑制する方法。 Irritation to the skin of a pest repellent in which at least one ether compound selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene diglyceryl ether and polyoxypropylene alkyl ether is applied to the skin together with the pest repellent How to suppress.
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