WO2023120346A1 - Antibacterial and antifungal composition - Google Patents

Antibacterial and antifungal composition Download PDF

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Publication number
WO2023120346A1
WO2023120346A1 PCT/JP2022/046145 JP2022046145W WO2023120346A1 WO 2023120346 A1 WO2023120346 A1 WO 2023120346A1 JP 2022046145 W JP2022046145 W JP 2022046145W WO 2023120346 A1 WO2023120346 A1 WO 2023120346A1
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test
antibacterial
amount
oil
component
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French (fr)
Japanese (ja)
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誠治 立花
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アース製薬株式会社
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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
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A01N25/06—Aerosols
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/04—Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/22—Phase substances, e.g. smokes, aerosols or sprayed or atomised substances

Definitions

  • the present invention relates to an antibacterial antifungal composition and a spray thereof.
  • the purpose of the present invention is to provide an antibacterial and antifungal composition and a spray thereof that can exhibit antimicrobial activity for a long period of time in a wet environment such as a bathroom.
  • the gist of the present invention is as follows. 1. An antibacterial and antifungal composition comprising (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component. 2.1. A spray containing the antibacterial and antifungal composition described in 1. above in a spray container.
  • Component (A) in the present invention is an oil-soluble antibacterial component.
  • the oil-soluble antibacterial component in the present invention means a component exhibiting antibacterial, antifungal, and antiviral activity with a water solubility of less than 1 w/w% at 25°C.
  • Component (A) in the present invention is preferably an antibacterial component with a water solubility of less than 0.1 w/w% at 25°C, more preferably less than 0.06 w/w%.
  • the water solubility in the present invention is calculated by EPI suite version 4.11, which is one of the physical property estimation software for chemical substances available from the United States Environmental Protection Agency (EPA). /w%).
  • Component (A) in the present invention is not particularly limited as long as it is the oil-soluble antibacterial component described above. compounds known to have antibacterial activity of In addition, antibacterial fragrance ingredients, environmental hygiene antibacterial ingredients such as 3-iodo-2-propynylbutylcarbamate (IPBC), capric acid monoglyceride, [(4-chlorophenoxy)methyl]3-iodo-2-propynyl ether, procymidone , bioreton, morestan and other agricultural chemical bactericidal components. Among them, phenol compounds and antibacterial fragrance ingredients are preferred as the component (A) in the present invention, since they can stably exert antibacterial and antifungal effects even in a wet environment. In addition, the component (A) in the present invention does not contain components with positive electrical properties such as cationic compounds.
  • Phenolic compounds suitable as the component (A) in the present invention are those having oil-soluble (water-insoluble) antibacterial activity and having a basic skeleton of a chemical structure in which one of the hydrogen atoms of benzene is substituted with a hydroxyl group. .
  • phenol compounds examples include alkyl-substituted phenols such as cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, cyclohexylphenol, xylenol, methylethylphenol, isopropylmethylphenol, and di-t-butylphenol;
  • alkyl ether derivatives of dihydric phenol such as eugenol, hydroxybenzoic acid such as methylparaben, ethylparaben, propylparaben, butylparaben, salicylic acid, and hydroxybenzoic acid alkyl ester derivatives such as methyl salicylate.
  • phenol compounds having no heteroatoms other than oxygen atoms are preferred, alkyl-substituted phenols are more preferred, and alkyl-substituted phenols substituted with one or two alkyl groups having 1 to 6 carbon atoms are more preferred, particularly , a dialkyl-substituted phenol substituted with two alkyl groups having 1 to 6 carbon atoms.
  • alkyl-substituted phenol isopropylmethylphenol is preferable.
  • 4-isopropyl-3- is preferred because high antibacterial, antifungal, and antiviral effects can be obtained by using it in combination with the cationic antibacterial component of component (B), which will be described later.
  • the water solubility at 25°C is 0.002 w/w% linalyl acetate, 0.0039 w/w% citronellal, 0.026 w/w% geraniol, 0.068 w/w% linalool, and 0.043 w/w menthol, respectively.
  • X ⁇ is a counterion.
  • R 5 is an alkyl group having 8 to 18 carbon atoms
  • X - is a counterion.
  • each R 6 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • each R 7 is independently a an alkylene group
  • R 8 is an alkylene group having 2 to 8 carbon atoms
  • each R 9 is independently an alkyl group having 1 to 18 carbon atoms
  • X 2- is a counterion.
  • any of the groups which may be the same or different from R 1 and have an alkyl group having 1 to 4 carbon atoms or 8 to 18 carbon atoms, a benzyl group, or an alkyl chain having 8 to 10 carbon atoms
  • An alkylphenyldiethoxy group is preferable, and an alkyl group having 8 to 18 carbon atoms, a benzyl group, and an alkylphenyldiethoxy group having an alkyl chain having 8 carbon atoms are more preferable.
  • R 3 and R 4 are alkyl groups having 1 to 4 carbon atoms, which may be the same or different, and are preferably methyl groups.
  • Specific examples of the compound represented by the general formula (3) include 1,4-bis(3,3′-(1-decylpyridinium)methyloxy)butane bromide, 1,4-bis(3,3 '-(1-decylpyridinium)methyloxy)butane chloride, 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane dimethosulfate and the like.
  • the spray member (spray button) in the present invention is a member that is attached to the pressure container via an aerosol valve for fixed quantity spray.
  • the spray button is formed with a passage in the operating part through which the aerosol composition taken from the pressure container passes through the stem hole of the aerosol valve for fixed quantity spray, and a nozzle hole through which the aerosol composition is sprayed.
  • the inner diameter of the nozzle of the spray button is preferably ⁇ 0.45 to 3.0 mm, more preferably ⁇ 0.5 to 2.0 mm, from the viewpoint of keeping the spray time within the desired range. , ⁇ 0.6 to 1.6 mm are more preferable.
  • a digital force gauge for example, manufactured by Imada Co., Ltd., model number: DS2-2N placed at a distance of 20 cm from the nozzle of the metered aerosol. It can be measured by calculating the average of the maximum value when the aerosol composition is sprayed toward the center of a circular flat plate with a diameter of ⁇ 60 mm attached to the device.
  • the metered dose aerosol in the present invention has a spraying time of 1 second or less in one spraying operation.
  • spraying an aerosol composition with a predetermined amount in the range of 0.1 to 3.0 mL per spray within 1 second (A) oil-soluble contained in the antibacterial antifungal composition of the present invention Since the diffusibility of the antibacterial component and (B) the cationic antibacterial component can be efficiently increased, (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component adhere to the object existing in the moist environment. It is believed that not only the amount but also the fixing amount can be improved.
  • the particle size of the antibacterial and antifungal composition when sprayed from the nozzle is not particularly limited, but if the average particle size at a spray distance of 50 cm from the nozzle is in the range of 5 ⁇ m or more and less than 100 ⁇ m, This is preferable in terms of improving not only the amount of adhesion to an object in a wet environment but also the amount of fixation.
  • the particle size means a numerical value measured by a particle size distribution measuring container. Specifically, from a position where the distance between the laser beam emitted from the laser light emitting part of the particle size distribution measurement container to the light receiving part and the injection port of the test sample is 50 cm, the sprayed matter passes through the laser beam perpendicularly.
  • the antibacterial and antifungal composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component contains deodorant components (flavonoids, etc.) and the like, as long as the effects of the present invention are not impaired.
  • a perfume component other than the antibacterial perfume component, etc. may be blended.
  • commonly used formulation aids such as liquid carriers, surfactants, solid carriers, antifreezing agents, antifoaming agents, antiseptics, etc. agents, antioxidants, perfume ingredients, antistatic agents, film-forming agents, thickeners and the like may be added.
  • Example 2 As shown in Table 2, the test specimens of Examples 1 and 2, which are specific examples of the antibacterial and antifungal composition of the present invention using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, were used in bathrooms in Japan.
  • the adhesion amount of (A) the oil-soluble antibacterial component to the test member of the mortar plate imitating the wall material is about 1.5 compared to the test specimen of Comparative Example 1 containing only the (A) oil-soluble antibacterial component It has been clarified that the efficiency is improved by about 1.9 times.
  • the obtained acetone cleaning solution was quantitatively analyzed by gas chromatography / high performance liquid chromatography, and (A) oil-soluble adhering to the test member
  • 4-isopropyl-3-methylphenol was analyzed by gas chromatography, and benzalkonium chloride was analyzed by high performance liquid chromatography. The test was performed in duplicate.
  • the amount of fixation of the test specimen of Example 1 which is a specific example of the antibacterial and antifungal composition of the present invention, which uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, is
  • the (B) cationic antibacterial component (BZC) on the test member of the mortar board imitating the wall material of a bathroom in Japan is 76% with respect to the adhesion amount of the (B) cationic antibacterial component (BZC) shown in Table 3.
  • the amount of fixation of the test specimen of Comparative Example 2 was about 40% of the amount of adhesion shown in Table 3.
  • Example 1 which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, was used for the wall of a bathroom in Japan.
  • the amount of (A) oil-soluble antibacterial component adhered to the FRP and mortar test members imitating wood is about 1.8 times that of the test specimen of Comparative Example 1 containing only (A) the oil-soluble antibacterial component.
  • a pressure can for aerosol (capacity 133 mL) is filled with 6 mL of each test sample stock solution of Example 3, Comparative Examples 3 and 4, and an aerosol valve (one spray amount 1 mL, stem hole (shape: rectangular, area 0.7 mm 2 (1.0 mm x 0.7 mm) x 2)) to close the aerosol pressure can.
  • an aerosol valve one spray amount 1 mL, stem hole (shape: rectangular, area 0.7 mm 2 (1.0 mm x 0.7 mm) x 2
  • 14 mL of liquefied petroleum gas (0.49 MPa (25° C.) was filled under pressure as a propellant.
  • Test specimen preparation of test specimen stock solution
  • the test specimens of Example 1 and Comparative Example 1 of the above-mentioned "adhesion amount improvement effect confirmation test-1" were used as the test specimen undiluted solutions.
  • a pressure can for aerosol (capacity 133 mL) is filled with 6 mL of each test sample stock solution of Example 1 and Comparative Example 1, and an aerosol valve (one spray amount 1 mL, stem hole (shape: rectangular, area 0.7 mm 2 (1 0 mm x 0.7 mm) x 2)) to close the aerosol pressure can.
  • Test method The same mortar plate (5 cm x 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above "Deposited amount improvement effect confirmation test-1", was used as a test member. Ten test members (a total of 20 pieces) were affixed to each of two locations on a ceiling and a side wall measuring .8m x 1.8m x height 2m. The humidity in the bathroom (25 ° C.) was adjusted to 90% or more, and 20 test members at two locations were sufficiently wetted with water. The test specimen is sprayed (once sprayed) from the entrance of each bathroom toward the center of the bathroom, and 30 minutes after the spray treatment, two test members on the ceiling and two test members on the side walls are collected.
  • Test specimens The following test specimens were prepared by adding 0.001 to 20 parts by weight of the oil-soluble antibacterial component (A) to 1 part by weight of the cationic antibacterial component (B).
  • the oil-soluble antibacterial component (A) shown in Table 11 below was diluted with ethanol to 13 w/v%, and diluted to 52 v/v% and purified water to 48 v/v%. This diluted solution was centrifuged (3500 rpm, 12 minutes), and the water layer part was added with (B) cationic antimicrobial component benzalkonium chloride or 1,4-bis(3,3'-(B) shown in Table 11 below.
  • Dibutyl phthalate was added as an internal standard to the obtained acetone cleaning solution, and quantitative analysis was performed by gas chromatography to analyze the amount (mg) of the (A) oil-soluble antibacterial component adhering to the test member.
  • the composition of each example test specimen a to f or comparative example test specimen a and the adhesion amount of (A) oil-soluble antibacterial component adhered to the test member are shown in Table 11 below as "adhesion amount (mg / test piece)". Shown together.
  • the example test specimen a which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, is a bathroom wall material in Japan.
  • the amount of (A) the oil-soluble antibacterial component attached to the test member of the mortar plate imitating the (A) compared to the comparative example test specimen a containing only the oil-soluble antibacterial component is improved by about 1.5 times. It became clear.
  • (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component were used in combination to suppress (A) the oil-soluble antibacterial component against objects present in a moist environment. It was confirmed that the effect of greatly improving the amount of the component attached was obtained.
  • test member was immersed in each (10 mL) of the test samples a to f of the examples and the test sample a of the comparative example, and mixed by inversion 10 times.
  • a test member taken out from each test specimen was immersed for 1 second in purified water (50 mL) stirred at 200 rpm, and thoroughly washed with about 5 mL of acetone.
  • Dibutyl phthalate was added as an internal standard to the obtained acetone cleaning solution, and quantitative analysis was performed by gas chromatography to analyze the amount (mg) of the (A) oil-soluble antibacterial component adhered to the test member.
  • Example test specimens a to f the amount of (A) fixed amount of oil-soluble antibacterial component is "fixed amount (mg/test piece)", and the percentage of the value obtained by dividing this fixed amount by the adhesion amount shown in Table 11 above ( %) is collectively shown in Table 12 below as “fixed amount/deposited amount (%)”.
  • Example test specimens c, d, e, and f used in the “adhesion amount/fixation amount improvement effect confirmation test-3” were used.
  • test specimens in which borneol in example test specimen d was replaced with linalool and 1,8-cineol were used in example test specimens g and j, and IPMP in example test specimen b was replaced with geraniol and camphor.
  • Example test sample k was obtained by replacing “BZC” of example test sample c with cetylpyridinium chloride in example test samples h and i.
  • test samples obtained by replacing “IPMP” of Comparative Example Test Specimen a with borneol, citronellal, linalool, geraniol, camphor, and 1,8-cineole were prepared as Comparative Example Test Specimens b, c, d, e, f, g.
  • Adhesion amount improvement effect confirmation test The same mortar plate (5 cm ⁇ 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above "Adhesion amount improvement effect confirmation test-1", was used as a test member.
  • test member is immersed in each (150 mL) of example test samples c to k or comparative example test samples b to g (150 mL) and each test solution is stirred for 10 minutes, and about 10 mL of acetone for washing is used.
  • Adhesion amount improvement effect confirmation test of the above "Adhesion amount/fixing amount improvement effect confirmation test-3".
  • Fixing amount improvement effect confirmation test The same mortar plate (5 cm ⁇ 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above “Adhesion amount improvement effect confirmation test-1”, was used as a test member.
  • test member was immersed in each (150 mL) of test samples c to k of Examples or test samples b to g of Comparative Examples, and each test solution was stirred for 10 minutes.
  • a test member taken out from each test solution was immersed for 1 second in purified water (300 mL) stirred at 200 times/min, and then thoroughly washed with about 10 mL of acetone.
  • the subsequent quantitative analysis was performed in the same manner as in "(3) Fixing amount improvement effect confirmation test" of the above "Adhesion amount/fixing amount improvement effect confirmation test-3".
  • composition of each example test specimen c to k or comparative example test specimen b to g, and the adhesion amount of (A) oil-soluble antibacterial component adhered to the test member is "adhesion amount (mg / test piece)", and the fixing amount is "Fixed amount (mg/test piece)” and the percentage (%) of the value obtained by dividing this fixed amount by the adhered amount is shown in Table 13 below as “Fixed amount/adhered amount (%)".
  • benzalkonium chloride is indicated as "BZC”
  • 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane bromide is indicated as "hygenia”
  • cetylpyridinium chloride is indicated as "CPC”.
  • example test specimens c to j which are specific examples of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, were used in bathrooms in Japan.
  • the adhesion amount of (A) the oil-soluble antibacterial component to the test member of the mortar plate imitating the wall material is about 1.1 compared to the comparative test specimens b to g containing only the (A) oil-soluble antibacterial component. It was clarified that it improved by ⁇ 1.3 times.
  • example test specimens c to k which are specific examples of the antibacterial and antifungal composition of the present invention, are the amount of (A) the oil-soluble antibacterial component fixed to the test member of a mortar plate imitating the wall material of a Japanese bathroom. was 58 to 87% of the adhesion amount.
  • the values of (A) the amount of fixation/adhesion (%) of the oil-soluble antibacterial component in Examples c to k correspond to the amounts of fixation/adhesion (%) of the (A) oil-soluble antibacterial component in Comparative Examples b to g. It was found to be 1.1 to 1.5 times as high as the amount (%) and to be excellent in fixability. That is, it was confirmed that even when an antibacterial fragrance component was employed as (A) the oil-soluble antibacterial component in the present invention, excellent fixability to objects existing in a wet environment could be achieved. In addition, it was also confirmed that compared to the comparative test specimens b to g containing only the antibacterial fragrance component as the (A) oil-soluble antibacterial component, the fixability to objects in a wet environment is excellent.
  • Test Specimen The test specimens of Example 1 and Comparative Example 1 used in the above-mentioned "adhesion amount improvement effect confirmation test-1" were used.
  • test members an acrylic resin plate (manufactured by Hikari Co., Ltd., Sumiholiday A000-2SS) and an ABS resin plate (manufactured by Nippon Test Panel Co., Ltd.), each measuring 5 cm ⁇ 5 cm, were used.
  • Test method 10 ⁇ L of each of the test specimens of Example 1 and Comparative Example 1 was dropped onto each test member and left for 5 minutes.
  • Example 1 did not have a large effect on the test member even though it contained (A) 4-isopropyl-3-methylphenol, which is an oil-soluble antibacterial component, as in Comparative Example 1.
  • (B) combined use with benzalkonium chloride, which is a cationic antibacterial component, 4-isopropyl-3-methylphenol was suppressed from penetrating into the interior of the test member and remained on the surface of the test member.
  • the (A) oil-soluble antibacterial component in the present invention may cause external effects such as whitening and swelling on plastic materials such as acrylic resins and ABS resins used for bathroom accessories and drains.

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Abstract

The present invention addresses the problem of providing an antibacterial and antifungal composition or a spray agent thereof which can exhibit antimicrobial activity for a long period of time in a humid environment such as a bathroom. To solve the problem, an antibacterial and antifungal composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component is provided.

Description

抗菌抗カビ組成物Antibacterial antifungal composition
　本発明は、抗菌抗カビ組成物及び、その噴霧剤に関する。 The present invention relates to an antibacterial antifungal composition and a spray thereof.
　住環境における微生物汚染が問題となりやすい場所として、湿度が高く湿潤な状態が維持されやすい浴室や、頻繁に水が供給される台所シンク・洗面所・トイレなどの水まわり、結露を生じやすい窓や壁などが挙げられる。このような環境では、微生物の生育に必要な水分が潤沢に存在していることから、微生物汚染は速やかに進行するのみならず、防除を実施しても、微生物の生育に適した環境が維持されるため、微生物は何度も繰り返し発生してしまう。
　これらの微生物防除のために様々な方法が検討されており、主な方法の１つとして、微生物による汚染箇所に抗菌剤を処理する方法が知られている。抗菌剤は、大きく水溶性と油溶性（非水溶性）に分類でき、水溶性の抗菌剤としてはモノ又はビス型のカチオン型抗菌成分などが、油溶性（非水溶性）の抗菌剤としてはイソプロピルメチルフェノールなどフェノール化合物などが挙げられる。しかしながら、水溶性の抗菌剤は水に溶解して水と共に流失してしまい、微生物の生育に適した湿潤環境では、長期間にわたり抗菌効果を発揮することが難しいという問題がある。
　一方、油溶性（非水溶性）の抗菌剤は、処理表面に均一に付着すれば水による流失が生じにくく、長期間にわたり抗菌効果を発揮する特性があるものの、処理表面に存在する水分が障害となり、抗菌剤が付着しにくいという問題もある。これは、油溶性（非水溶性）の抗菌剤が処理表面上の水により処理表面に付着出来ないだけでなく、溶液中の油溶性（非水溶性）の抗菌剤が、処理表面上の水により結晶又は油滴を形成してしまうことに起因する。結果として、油溶性（非水溶性）の抗菌剤は処理表面から容易に脱落し、長期間にわたり抗菌効果を発揮することが難しいという問題もあった。
　これらの問題を解決するため、湿潤な環境で抗菌剤の効果を発揮させるためには、特殊な展着剤で処置面に固定化する（例えば、特許文献１）ほか、ゼオライト等の担持体に含浸させて薬剤を徐放化させる（例えば、特許文献２）などの、複雑な手法を選択する必要があった。 Places where microbial contamination in the living environment is likely to be a problem include bathrooms where humidity is high and tends to be maintained in a moist state, water-related areas such as kitchen sinks, washrooms, and toilets where water is frequently supplied, and windows where condensation is likely to occur. walls, etc. In such an environment, there is plenty of moisture necessary for the growth of microorganisms, so microbial contamination not only progresses quickly, but even if control is implemented, an environment suitable for the growth of microorganisms is maintained. As a result, microorganisms are generated over and over again.
Various methods have been investigated for controlling these microorganisms, and one of the known methods is to apply an antibacterial agent to a portion contaminated with microorganisms. Antibacterial agents can be roughly classified into water-soluble and oil-soluble (non-water-soluble). Examples include phenolic compounds such as isopropylmethylphenol. However, the water-soluble antibacterial agent dissolves in water and is washed away with the water, and in a moist environment suitable for the growth of microorganisms, it is difficult to exhibit antibacterial effects over a long period of time.
On the other hand, oil-soluble (water-insoluble) antibacterial agents are less likely to be washed away by water if they adhere evenly to the treated surface, and have the property of exhibiting antibacterial effects over a long period of time. As a result, there is also a problem that the antibacterial agent is difficult to adhere. This is because not only is the oil-soluble (water-insoluble) antibacterial agent unable to adhere to the treated surface due to the water on the treated surface, but also the oil-soluble (water-insoluble) antibacterial agent in solution is absorbed by the water on the treated surface. This is due to the formation of crystals or oil droplets due to As a result, the oil-soluble (water-insoluble) antibacterial agent is easily removed from the treated surface, making it difficult to exert antibacterial effects over a long period of time.
In order to solve these problems, in order to exert the effect of the antibacterial agent in a moist environment, it is fixed on the treatment surface with a special spreading agent (for example, Patent Document 1), and on a carrier such as zeolite. It was necessary to choose a complicated technique such as impregnation to release the drug slowly (eg, Patent Document 2).
特開２０１７－１６０１３６号公報JP 2017-160136 A 特開平０７－３０９７０６号公報JP-A-07-309706
　本発明は、浴室など湿潤な環境において長期間にわたり抗微生物活性を発揮させ得る、抗菌抗カビ組成物やその噴霧剤の提供を目的としている。 The purpose of the present invention is to provide an antibacterial and antifungal composition and a spray thereof that can exhibit antimicrobial activity for a long period of time in a wet environment such as a bathroom.
　本発明者らは、より簡便に非水溶性の抗微生物剤を湿潤環境に存在する対象物に付着させ、抗微生物効果を発現させるための手法を新たに検討した結果、（Ａ）油溶性抗菌成分と（Ｂ）カチオン型抗菌成分を併用することで、非水溶性である成分（Ａ）の油溶性抗菌成分の処理表面への付着量及び定着量が湿潤環境下において向上することを見出し、本発明を完成するに至ったものである。 The present inventors have newly studied a method for more easily attaching a water-insoluble antimicrobial agent to an object existing in a wet environment and expressing an antimicrobial effect. As a result, (A) oil-soluble antimicrobial By using the component (B) in combination with the cationic antibacterial component, the amount of adhesion and fixation of the oil-soluble antibacterial component (A), which is water-insoluble, to the treated surface is improved in a wet environment. The present invention has been completed.
　本発明は、詳しくは以下の事項を要旨とする。
１．（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を含有する、抗菌抗カビ組成物。
２．１．に記載の抗菌抗カビ組成物を噴霧容器に充填した、噴霧剤。 In detail, the gist of the present invention is as follows.
1. An antibacterial and antifungal composition comprising (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component.
2.1. A spray containing the antibacterial and antifungal composition described in 1. above in a spray container.
　本発明の抗菌抗カビ組成物は、非水溶性の抗微生物剤である成分（Ａ）の油溶性抗菌成分のみならず、水溶性の抗微生物剤である成分（Ｂ）のカチオン型抗菌成分をも、湿潤環境に存在する対象物への付着量を向上させることができ、さらに、湿潤環境に存在する対象物への定着量をも向上させることができるので、長期間にわたり抗微生物効果を得ることができ極めて有用である。
　また、本発明の噴霧剤は、簡便に湿潤環境に存在する対象物に抗菌抗カビ組成物を付着、定着させることが可能なため、非常に有用である。 The antibacterial and antifungal composition of the present invention contains not only the oil-soluble antibacterial component (A), which is a water-insoluble antimicrobial agent, but also the cationic antibacterial component (B), which is a water-soluble antimicrobial agent. can also improve the amount of adhesion to objects present in a wet environment, and can also improve the amount of fixation to objects present in a wet environment, so that antimicrobial effects can be obtained over a long period of time. It is extremely useful.
In addition, the spray of the present invention is very useful because it allows the antibacterial and antifungal composition to be easily adhered to and fixed to an object existing in a wet environment.
実施例の「効力持続実地評価試験」における、実施例３の定量噴霧型エアゾール試験検体を噴霧処理する浴室５カ所のうち、２カ所（浴室Ａ、Ｂ）の実地評価試験開始前と、実地評価試験開始時から８週後の浴室内の写真である。Before the start of the field evaluation test and the field evaluation of two of the five bathrooms (bathrooms A and B) where the fixed-quantity spray type aerosol test specimen of Example 3 was sprayed in the "field evaluation test of sustained effect" of the example It is a photograph in the bathroom 8 weeks after the start of the test.
　以下、本発明について詳細に説明する。
＜成分（Ａ）＞
　本発明における成分（Ａ）は、油溶性抗菌成分である。本発明における油溶性抗菌成分とは、２５℃の水溶解度が１ｗ／ｗ％未満の抗菌・抗カビ・抗ウイルス活性を発揮する成分を意味する。本発明における成分（Ａ）は、２５℃の水溶解度が０．１ｗ／ｗ％未満の抗菌成分であることが好ましく、０．０６ｗ／ｗ％未満の抗菌成分であることがより好ましい。本発明における水溶解度は、米国環境保護庁（ＥＰＡ）から入手できる化学物質の物性推算ソフトウェアの１つであるＥＰＩ　ｓｕｉｔｅ　ｖｅｒｓｉｏｎ４．１１により計算したＷａｔｅｒ　Ｓｏｌｕｂｉｌｉｔｙの値（ｍｇ／Ｌ）を重量％（ｗ/ｗ％）に換算したものとする。
　本発明における成分（Ａ）としては、上記の油溶性抗菌成分であれば特に制限はないが、例えば、フェノール骨格を有するフェノール化合物、テブコナゾール、チアベンダゾール、エニルコナゾール、サイアベンダゾール等のアゾール化合物等の抗菌活性を有することが公知である化合物が挙げられる。また、抗菌性香料成分、３－ヨード－２－プロピニルブチルカーバメート（ＩＰＢＣ）、カプリン酸モノグリセリド、［（４－クロロフェノキシ）メチル］３－ヨード－２－プロピニルエーテル等の環境衛生用抗菌成分、プロシミドン、バイレトン、モレスタン等の農業用薬剤殺菌成分等が挙げられる。中でも、本発明における成分（Ａ）としては、湿潤環境でも安定して抗菌抗カビ効果を発揮することができる点において、フェノール化合物、抗菌性香料成分が好ましい。
　なお、本発明における成分（Ａ）は、カチオン化合物などプラスの電気性質を帯びた成分は含まない。 The present invention will be described in detail below.
<Component (A)>
Component (A) in the present invention is an oil-soluble antibacterial component. The oil-soluble antibacterial component in the present invention means a component exhibiting antibacterial, antifungal, and antiviral activity with a water solubility of less than 1 w/w% at 25°C. Component (A) in the present invention is preferably an antibacterial component with a water solubility of less than 0.1 w/w% at 25°C, more preferably less than 0.06 w/w%. The water solubility in the present invention is calculated by EPI suite version 4.11, which is one of the physical property estimation software for chemical substances available from the United States Environmental Protection Agency (EPA). /w%).
Component (A) in the present invention is not particularly limited as long as it is the oil-soluble antibacterial component described above. compounds known to have antibacterial activity of In addition, antibacterial fragrance ingredients, environmental hygiene antibacterial ingredients such as 3-iodo-2-propynylbutylcarbamate (IPBC), capric acid monoglyceride, [(4-chlorophenoxy)methyl]3-iodo-2-propynyl ether, procymidone , bioreton, morestan and other agricultural chemical bactericidal components. Among them, phenol compounds and antibacterial fragrance ingredients are preferred as the component (A) in the present invention, since they can stably exert antibacterial and antifungal effects even in a wet environment.
In addition, the component (A) in the present invention does not contain components with positive electrical properties such as cationic compounds.
　本発明における成分（Ａ）として好適なフェノール化合物は、油溶性（非水溶性）の抗菌活性を有するもので、ベンゼンの水素原子の１つが水酸基に置換した化学構造を基本骨格とする化合物である。このようなフェノール化合物としては、例えば、クレゾール、エチルフェノール、プロピルフェノール、ブチルフェノール、ペンチルフェノール、ヘキシルフェノール、シクロヘキシルフェノール、キシレノール、メチルエチルフェノール、イソプロピルメチルフェノール、ジ－ｔ－ブチルフェノール等のアルキル置換フェノール、オイゲノール等の２価フェノールのアルキルエーテル誘導体、メチルパラベン、エチルパラベン、プロピルパラベン、ブチルパラベン、サリチル酸等のヒドロキシ安息香酸やサリチル酸メチル等のヒドロキシ安息香酸アルキルエステル誘導体などが挙げられる。
　これらの中でも、酸素原子以外にヘテロ原子を有さないフェノール化合物が好ましく、アルキル置換フェノールがより好ましく、炭素数１～６のアルキル基が１つ又は２つ置換したアルキル置換フェノールがさらに好ましく、特に、炭素数１～６のアルキル基が２つ置換したジアルキル置換フェノールが好ましい。アルキル置換フェノールとして、イソプロピルメチルフェノールが好ましく、中でも、後述する成分（Ｂ）のカチオン型抗菌成分との併用により高い抗菌・抗カビ・抗ウイルス効果が得られるという点から、４－イソプロピル－３－メチルフェノール（ＩＰＭＰ）、２－イソプロピル－５－メチルフェノール（チモール）、５－イソプロピル－２－メチルフェノール（カルバクロール）のいずれか１種以上であることがより好ましい。また、２５℃の水溶解度は、それぞれＩＰＭＰ０．０２８６ｗ／ｗ％、チモール０．０４４ｗ／ｗ％、カルバクロール０．０３０ｗ／ｗ％である。 Phenolic compounds suitable as the component (A) in the present invention are those having oil-soluble (water-insoluble) antibacterial activity and having a basic skeleton of a chemical structure in which one of the hydrogen atoms of benzene is substituted with a hydroxyl group. . Examples of such phenol compounds include alkyl-substituted phenols such as cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, cyclohexylphenol, xylenol, methylethylphenol, isopropylmethylphenol, and di-t-butylphenol; Examples include alkyl ether derivatives of dihydric phenol such as eugenol, hydroxybenzoic acid such as methylparaben, ethylparaben, propylparaben, butylparaben, salicylic acid, and hydroxybenzoic acid alkyl ester derivatives such as methyl salicylate.
Among these, phenol compounds having no heteroatoms other than oxygen atoms are preferred, alkyl-substituted phenols are more preferred, and alkyl-substituted phenols substituted with one or two alkyl groups having 1 to 6 carbon atoms are more preferred, particularly , a dialkyl-substituted phenol substituted with two alkyl groups having 1 to 6 carbon atoms. As the alkyl-substituted phenol, isopropylmethylphenol is preferable. Among them, 4-isopropyl-3- is preferred because high antibacterial, antifungal, and antiviral effects can be obtained by using it in combination with the cationic antibacterial component of component (B), which will be described later. More preferably, one or more of methylphenol (IPMP), 2-isopropyl-5-methylphenol (thymol), and 5-isopropyl-2-methylphenol (carbacrol). Also, the water solubility at 25° C. is IPMP 0.0286 w/w %, thymol 0.044 w/w %, and carvacrol 0.030 w/w %, respectively.
　本発明における成分（Ａ）として好適な抗菌性香料成分としては、例えば、酢酸リナリル、α－ピネン、β－ピネン、シトロネロール、シトロネラール、ゲラニオール、ネロール、シトラール(ゲラニアール)、ネラール、アネトール、リナロール、メントール、α－テルピネオール、テルピネン－４－オール、１，８－シネオール（ユーカリプトール）、カルボン、カンファー、メントン、ボルネオール、プラウノトール、ファルネソール、ネロリドール、α－ビサボロール、α－サンタロール、ミルセン、酢酸ゲラニル、酢酸メンチル、酢酸ボルニル、ペリルアルコール、ペリルアルデヒド、３－カレンオキシド（３，４－エポキシカラン）、クミンアルデヒド、ピペリトン、イソメントン、アルテミシニン、オイゲノール、サリチル酸メチル、チモキノン、ヒノキチオール、シンナムアルデヒド、ｐ－アニスアルデヒド、ゲルマクレンＤ、β－カリオフィレン、安息香酸ゲラニル、リモネン、酢酸シトロネリル、酢酸メンタニル、酢酸テルピニル、メントフラン、酢酸イソボルニル、６－ジンゲロール、ヘリオナール、安息香酸、安息香酸メチル、α－サントニン、シス－３－ヘキセナール等が挙げられる。
　これらの中でも、本発明における成分（Ａ）として、酢酸リナリル、α－ピネン、β－ピネン、シトロネロール、シトロネラール、ゲラニオール、ネロール、シトラール（ゲラニアール）、ネラール、アネトール、リナロール、メントール、α－テルピネオール、テルピネン－４－オール、１，８－シネオール（ユーカリプトール）、カルボン、カンファー、メントン、ボルネオール、プラウノトール、ファルネソール、ネロリドール、α－ビサボロール、α－サンタロール、ミルセン、酢酸ゲラニル、酢酸メンチル、酢酸ボルニル、ペリルアルコール、ペリルアルデヒド、３－カレンオキシド（３，４－エポキシカラン）、クミンアルデヒド、ピペリトン、イソメントン、アルテミシニン、オイゲノール、サリチル酸メチル、チモキノン、ヒノキチオール、シンナムアルデヒド、ｐ－アニスアルデヒドが好ましく、酢酸リナリル、α－ピネン、β－ピネン、シトロネロール、シトロネラール、ゲラニオール、ネロール、シトラール（ゲラニアール）、ネラール、アネトール、リナロール、メントール、α－テルピネオール、テルピネン－４－オール、１，８－シネオール（ユーカリプトール）、カルボン、カンファー、メントン、ボルネオールがより好ましい。後述する成分（Ｂ）のカチオン型抗菌成分と併用した際に抗菌活性が高まりやすいという点から、酢酸リナリル、シトロネラール、ゲラニオール、リナロール、メントール、１，８－シネオール（ユーカリプトール）、カンファー、メントン、ボルネオールがさらに好ましい。また、２５℃の水溶解度は、それぞれ、酢酸リナリル０．００２ｗ／ｗ％、シトロネラール０．００３９ｗ／ｗ％、ゲラニオール０．０２６ｗ／ｗ％、リナロール０．０６８ｗ／ｗ％、メントール０．０４３ｗ／ｗ％、１，８－シネオール０．０３３ｗ／ｗ％、カンファー０．０３４ｗ／ｗ％、メントン０．０１８ｗ／ｗ％、ボルネオール０．１２ｗ／ｗ％である。
　後述する実施例において詳細に説明するが、本発明における成分（Ａ）の油溶性抗菌成分は、成分（Ｂ）のカチオン型抗菌成分と併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、成分（Ｂ）のカチオン型抗菌成分の付着量向上剤及び／又は定着量向上剤としての機能を発揮するものである。
　本発明における成分（Ａ）の油溶性抗菌成分は、抗菌抗カビ組成物全体に対して、０．０１～４０重量％含有することが好ましい。０．０１重量％以上とすることで抗菌抗カビ効果が得られる点において好ましく、４０重量％以下とすることで、成分（Ａ）の油溶性抗菌成分のにおいを使用上問題ない程度にすることができる点において好ましい。成分（Ａ）の油溶性抗菌成分は、抗菌抗カビ効果と使用時のにおいのバランスから、０．０５～３０重量％含有することがより好ましく、０．１～１５重量％含有することがさらに好ましい。 Examples of antibacterial perfume ingredients suitable as component (A) in the present invention include linalyl acetate, α-pinene, β-pinene, citronellol, citronellal, geraniol, nerol, citral (geranial), neral, anethole, linalool, and menthol. , α-terpineol, terpinen-4-ol, 1,8-cineole (eucalyptol), carvone, camphor, menthone, borneol, plaunotol, farnesol, nerolidol, α-bisabolol, α-santalol, myrcene, geranyl acetate , menthyl acetate, bornyl acetate, peryl alcohol, perillaldehyde, 3-carene oxide (3,4-epoxycarane), cuminaldehyde, piperitone, isomenthone, artemisinin, eugenol, methyl salicylate, thymoquinone, hinokitiol, cinnamaldehyde, p-anis Aldehyde, germacrene D, β-caryophyllene, geranyl benzoate, limonene, citronellyl acetate, menthanyl acetate, terpinyl acetate, menthofuran, isobornyl acetate, 6-gingerol, helional, benzoic acid, methyl benzoate, α-santonin, cis-3 - includes hexenal and the like.
Among these, as component (A) in the present invention, linalyl acetate, α-pinene, β-pinene, citronellol, citronellal, geraniol, nerol, citral (geranial), neral, anethole, linalool, menthol, α-terpineol, terpinene -4-ol, 1,8-cineol (eucalyptol), carvone, camphor, menthone, borneol, plaunotol, farnesol, nerolidol, α-bisabolol, α-santalol, myrcene, geranyl acetate, menthyl acetate, bornyl acetate , peryl alcohol, perillaldehyde, 3-carene oxide (3,4-epoxycaran), cuminaldehyde, piperitone, isomenthone, artemisinin, eugenol, methyl salicylate, thymoquinone, hinokitiol, cinnamaldehyde, p-anisaldehyde are preferred, and linalyl acetate , α-pinene, β-pinene, citronellol, citronellal, geraniol, nerol, citral (geranial), neral, anethole, linalool, menthol, α-terpineol, terpinen-4-ol, 1,8-cineole (eucalyptol) , carvone, camphor, menthone and borneol are more preferred. Linalyl acetate, citronellal, geraniol, linalool, menthol, 1,8-cineol (eucalyptol), camphor, menthone, because antibacterial activity tends to increase when used in combination with the cationic antibacterial ingredient of component (B) described later. , and borneol are more preferred. In addition, the water solubility at 25°C is 0.002 w/w% linalyl acetate, 0.0039 w/w% citronellal, 0.026 w/w% geraniol, 0.068 w/w% linalool, and 0.043 w/w menthol, respectively. %, 1,8-cineole 0.033 w/w %, camphor 0.034 w/w %, menthone 0.018 w/w %, borneol 0.12 w/w %.
As will be described in detail in the examples below, the oil-soluble antibacterial component of component (A) in the present invention can be used in combination with the cationic antibacterial component of component (B) to provide antibacterial and antibacterial properties to objects existing in a moist environment. It functions as an adhesion amount improver and/or an adhesion amount improver for the cationic antibacterial component (B) on the mold composition adhering surface.
The oil-soluble antibacterial component (A) in the present invention is preferably contained in an amount of 0.01 to 40% by weight based on the total antibacterial and antifungal composition. A content of 0.01% by weight or more is preferable in that an antibacterial and antifungal effect can be obtained. It is preferable in that it can be The oil-soluble antibacterial ingredient of component (A) is more preferably contained in an amount of 0.05 to 30% by weight, more preferably 0.1 to 15% by weight, from the viewpoint of the balance between the antibacterial antifungal effect and the odor during use. preferable.
＜成分（Ｂ）＞
　本発明における成分（Ｂ）は、カチオン型抗菌成分である。
　本発明のカチオン型抗菌成分は、下記一般式（１）、（２）及び（３）で表される抗菌・抗カビ・抗ウイルス活性を有する化合物を意味する。
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１は炭素数８～１８のアルキル基であり、Ｒ２は炭素数１～１８のアルキル基、ベンジル基又は炭素数１～１０のアルキル鎖を有するアルキルフェニルジエトキシ基の何れかであり、Ｒ３とＲ４は炭素数１～４のアルキル基である。Ｒ１とＲ２は同一であっても異なっていてもよく、Ｒ３とＲ４は同一であっても異なっていてもよい。Ｘ－は対イオンである。）
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ５は炭素数８～１８のアルキル基であり、Ｘ－は対イオンである。）
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ６は各々独立して水素原子、ハロゲン原子、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基であり、Ｒ７は各々独立して炭素数１～４のアルキレン基であり、Ｒ８は炭素数２～８のアルキレン基であり、Ｒ９は各々独立して炭素数１～１８のアルキル基であり、Ｘ２－は対イオンである。） <Component (B)>
Component (B) in the present invention is a cationic antibacterial component.
The cationic antibacterial component of the present invention means a compound having antibacterial, antifungal, and antiviral activities represented by the following general formulas (1), (2) and (3).
Figure JPOXMLDOC01-appb-C000001
 (In the formula, R 1 is an alkyl group having 8 to 18 carbon atoms, and R 2 is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyldiethoxy group having an alkyl chain having 1 to 10 carbon atoms. and R 3 and R 4 are alkyl groups having 1 to 4 carbon atoms, R 1 and R 2 may be the same or different, R 3 and R 4 may be the same or different. X − is a counterion.)
Figure JPOXMLDOC01-appb-C000002
 (Wherein, R 5 is an alkyl group having 8 to 18 carbon atoms, and X - is a counterion.)
Figure JPOXMLDOC01-appb-C000003
 (In the formula, each R 6 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and each R 7 is independently a an alkylene group, R 8 is an alkylene group having 2 to 8 carbon atoms, each R 9 is independently an alkyl group having 1 to 18 carbon atoms, and X 2- is a counterion.)
　一般式（１）において、Ｒ１は炭素数８～１８のアルキル基であり、Ｒ２は炭素数１～１８のアルキル基、ベンジル基又は炭素数１～１０のアルキル鎖を有するアルキルフェニルジエトキシ基の何れかであって、Ｒ１と同一であっても異なっていてもよく、炭素数１～４又は炭素数８～１８のアルキル基、ベンジル基、炭素数８～１０のアルキル鎖を有するアルキルフェニルジエトキシ基が好ましく、炭素数８～１８のアルキル基、ベンジル基、炭素数８のアルキル鎖を有するアルキルフェニルジエトキシ基がより好ましい。また、Ｒ３とＲ４は炭素数１～４のアルキル基であって、同一であっても異なっていてもよく、メチル基が好ましい。Ｘ－は対イオンであり、対イオンとしては、フッ素イオン、塩化物イオン、臭化物イオン等のハロゲンイオン、酢酸イオン、メタンスルホン酸イオン、トリフルオロメタンスルホン酸イオン、トルエンスルホン酸イオン等の有機酸イオンが挙げられる。
　一般式（１）で表される化合物の具体例としては、例えば、塩化ラウリルトリメチルアンモニウム、臭化ラウリルトリメチルアンモニウム、塩化ミリスチルトリメチルアンモニウム、臭化ミリスチルトリメチルアンモニウム、塩化セチルトリメチルアンモニウム、臭化セチルトリメチルアンモニウム、塩化ステアリルトリメチルアンモニウム、臭化ステアリルトリメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化ジデシルジメチルアンモニウム、ジデシルジメチルアンモニウムメトサルフェート、塩化ジラウリルジメチルアンモニウム、塩化ジミリスチルジメチルアンモニウム、塩化ジセチルジメチルアンモニウム、ジラウリルジメチルアンモニウムメトサルフェート、塩化ジステアリルジメチルアンモニウム、ジステアリルジメチルアンモニウムメトサルフェート、塩化ベンゼトニウム、ベンゼトニウムメトサルフェート、塩化ベンザルコニウム、ベンザルコニウムメトサルフェート、サッカリン酸ベンザルコニウム等が挙げられる。
　一般式（２）において、Ｒ５は炭素数８～１８のアルキル基である。Ｘ－は対イオンであり、対イオンとしては、フッ素イオン、塩化物イオン、臭化物イオン等のハロゲンイオン、酢酸イオン、メタンスルホン酸イオン、トリフルオロメタンスルホン酸イオン、トルエンスルホン酸イオン等の有機酸イオンが挙げられる。
　一般式（２）で表される化合物の具体例としては、例えば、塩化セチルピリジニウム、セチルピリジニウムメトサルフェート等が挙げられる。
　一般式（３）において、Ｒ６は各々独立して水素原子、ハロゲン原子、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基であり、水素原子であることが好ましく、Ｒ７は各々独立して炭素数１～４のアルキレン基であり、各々ピリジン環の３位又は４位に結合しているメチレン基であることが好ましく、Ｒ８は炭素数２～８のアルキレン基であり、テトラメチレン基であることが好ましく、Ｒ９は各々独立して炭素数１～１８のアルキル基であり、オクチル基、デシル基及びドデシル基から選ばれる基であることが好ましい。Ｘ２－は対イオンであり、この対イオンとしては、フッ素イオン、塩化物イオン、臭化物イオン等の２つのハロゲンイオン、酢酸イオン、メタンスルホン酸イオン、トリフルオロメタンスルホン酸イオン、トルエンスルホン酸イオン等の２つの有機酸イオン、硫酸イオンが挙げられる。
　一般式（３）で表される化合物の具体例としては、例えば、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン塩化物、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタンジメトサルフェート等が挙げられる。 In general formula (1), R 1 is an alkyl group having 8 to 18 carbon atoms, and R 2 is an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an alkylphenyl diethoxy having an alkyl chain having 1 to 10 carbon atoms. any of the groups, which may be the same or different from R 1 and have an alkyl group having 1 to 4 carbon atoms or 8 to 18 carbon atoms, a benzyl group, or an alkyl chain having 8 to 10 carbon atoms An alkylphenyldiethoxy group is preferable, and an alkyl group having 8 to 18 carbon atoms, a benzyl group, and an alkylphenyldiethoxy group having an alkyl chain having 8 carbon atoms are more preferable. Also, R 3 and R 4 are alkyl groups having 1 to 4 carbon atoms, which may be the same or different, and are preferably methyl groups. X − is a counter ion, and the counter ions include halogen ions such as fluoride ion, chloride ion and bromide ion, organic acid ions such as acetate ion, methanesulfonate ion, trifluoromethanesulfonate ion and toluenesulfonate ion. is mentioned.
Specific examples of the compound represented by formula (1) include lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, myristyltrimethylammonium chloride, myristyltrimethylammonium bromide, cetyltrimethylammonium chloride, and cetyltrimethylammonium bromide. , stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, dilauryldimethylammonium chloride, dimyristyldimethylammonium chloride, dicetyldimethylammonium chloride, dilauryl dimethylammonium methosulfate, distearyldimethylammonium chloride, distearyldimethylammonium methosulfate, benzethonium chloride, benzethonium methosulfate, benzalkonium chloride, benzalkonium methosulfate, benzalkonium saccharinate and the like.
In general formula (2), R 5 is an alkyl group having 8 to 18 carbon atoms. X − is a counter ion, and the counter ions include halogen ions such as fluoride ion, chloride ion and bromide ion, organic acid ions such as acetate ion, methanesulfonate ion, trifluoromethanesulfonate ion and toluenesulfonate ion. is mentioned.
Specific examples of the compound represented by formula (2) include cetylpyridinium chloride, cetylpyridinium methosulfate, and the like.
In general formula (3), each R 6 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, preferably a hydrogen atom, and R 7 are each independently an alkylene group having 1 to 4 carbon atoms, each preferably a methylene group bonded to the 3- or 4-position of the pyridine ring, and R 8 is an alkylene group having 2 to 8 carbon atoms. , preferably a tetramethylene group, and each R 9 is independently an alkyl group having 1 to 18 carbon atoms, preferably a group selected from an octyl group, a decyl group and a dodecyl group. X 2- is a counter ion, and examples of the counter ion include two halogen ions such as fluoride ion, chloride ion, and bromide ion, acetate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, and the like. and two organic acid ions, a sulfate ion.
Specific examples of the compound represented by the general formula (3) include 1,4-bis(3,3′-(1-decylpyridinium)methyloxy)butane bromide, 1,4-bis(3,3 '-(1-decylpyridinium)methyloxy)butane chloride, 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane dimethosulfate and the like.
　本発明のカチオン型抗菌成分としては、高い抗菌活性を有するとともに、湿潤環境に存在する対象物に対し、高い付着性を有する点から、臭化セチルトリメチルアンモニウム、塩化ジデシルジメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化ベンザルコニウム、ベンザルコニウムメトサルフェート、サッカリン酸ベンザルコニウム、塩化ベンゼトニウム、ベンゼトニウムメトサルフェート、塩化セチルピリジニウム、セチルピリジニウムメトサルフェート、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物が好ましく、塩化ジデシルジメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化セチルピリジニウム、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物が特に好ましい。
　後述する実施例において詳細に説明するが、本発明における成分（Ｂ）のカチオン型抗菌成分は、本発明における成分（Ａ）の油溶性抗菌成分、特に、フェノール化合物及び／又は抗菌性香料成分と併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、成分（Ａ）の油溶性抗菌成分であるフェノール化合物及び／又は抗菌性香料成分の付着量向上剤及び／又は定着量向上剤としての機能を発揮するものである。
　本発明における成分（Ｂ）のカチオン型抗菌成分は、抗菌抗カビ組成物全体に対して、０．０１～４０重量％含有することが好ましい。０．０１重量％以上とすることで抗菌抗カビ効果が得られる点において好ましく、４０重量％以下とすることで、成分（Ｂ）のカチオン型抗菌成分による粘膜への刺激を使用上問題ない程度にすることができる点において好ましい。成分（Ｂ）のカチオン型抗菌成分は、抗菌抗カビ効果と使用時の粘膜への刺激のバランスから、抗菌抗カビ組成物全体に対して、０．０５～３５重量％含有することがより好ましく、抗菌抗カビ組成物全体に対して、０．１～３０重量％含有することがさらに好ましい。 As the cationic antibacterial component of the present invention, cetyltrimethylammonium bromide, didecyldimethylammonium chloride, and dioctyldimethyl chloride are selected from the viewpoint of having high antibacterial activity and high adhesion to objects existing in a wet environment. ammonium, benzalkonium chloride, benzalkonium methosulfate, benzalkonium saccharinate, benzethonium chloride, benzethonium methosulfate, cetylpyridinium chloride, cetylpyridinium methosulfate, 1,4-bis(3,3'-(1-decyl Pyridinium)methyloxy)butane bromide is preferred, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, 1,4-bis(3,3′-(1-decylpyridinium) Methyloxy)butane bromide is particularly preferred.
As described in detail in the examples below, the cationic antibacterial component of component (B) in the present invention is an oil-soluble antibacterial component of component (A) in the present invention, in particular, a phenol compound and / or an antibacterial fragrance component. When used in combination, it is an agent for improving the amount of adhesion of the phenol compound, which is an oil-soluble antibacterial component of component (A), and/or an antibacterial fragrance component on the surface of an object in a moist environment on which the antibacterial and antifungal composition adheres. Alternatively, it exhibits a function as a fixing amount improver.
The content of the cationic antibacterial component (B) in the present invention is preferably 0.01 to 40% by weight based on the total antibacterial and antifungal composition. When it is 0.01% by weight or more, it is preferable in that antibacterial and antifungal effects can be obtained. It is preferable in that it can be The cationic antibacterial component (B) is more preferably contained in an amount of 0.05 to 35% by weight based on the total antibacterial and antifungal composition in terms of the balance between antibacterial and antifungal effects and irritation to mucous membranes during use. , more preferably 0.1 to 30% by weight based on the total antibacterial and antifungal composition.
　本発明の抗菌抗カビ組成物における、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分の各含有量は、適用剤型や適用環境において適宜決定すれば良いが、（Ｂ）カチオン型抗菌成分１重量部に対して、（Ａ）油溶性抗菌成分を０．００１～２０重量部とするのが好ましく、より好ましくは０．０１～１０重量部、さらに好ましくは１～７重量部となるように配合する。
　例えば、（Ａ）油溶性抗菌成分として４－イソプロピル－３－メチルフェノール（ＩＰＭＰ）を、（Ｂ）カチオン型抗菌成分として塩化ベンザルコニウムを選択した場合、塩化ベンザルコニウム１重量部に対し、４－イソプロピル－３－メチルフェノール（ＩＰＭＰ）を０．０１～１０重量部とする抗菌抗カビ組成物が、湿潤環境に存在する対象物への付着量のみならず、定着量を向上させる効果を得るために好ましい。 The contents of (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component in the antibacterial/antifungal composition of the present invention may be appropriately determined depending on the application type and application environment. (A) The oil-soluble antibacterial component is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 1 to 7 parts by weight, relative to 1 part by weight of the antibacterial ingredient. Mix as much as possible.
For example, when (A) 4-isopropyl-3-methylphenol (IPMP) is selected as an oil-soluble antimicrobial component and (B) benzalkonium chloride is selected as a cationic antimicrobial component, 1 part by weight of benzalkonium chloride is An antibacterial antifungal composition containing 0.01 to 10 parts by weight of 4-isopropyl-3-methylphenol (IPMP) has the effect of improving not only the amount of adhesion to an object in a wet environment but also the amount of fixation. preferred to obtain.
＜製剤型＞
　本発明の抗菌抗カビ組成物は、各種製剤として用いることができる。製剤としては、例えば、油剤、乳剤、水和剤、フロアブル剤（水中懸濁剤、水中乳濁剤等）、マイクロカプセル剤、粉剤、粒剤、錠剤、液剤、ゲル剤、ゾル剤、ピエゾ式製剤、送風式製剤、スプレー剤、エアゾール剤等が挙げられる。
　中でも、スプレー剤やエアゾール剤等の噴霧剤が、湿潤環境に存在する対象物への本発明の抗菌抗カビ組成物の付着量のみならず定着量をも向上させる点において好適である。また、簡便な製剤型として有用である。スプレー剤やエアゾール剤とするには、所定の噴霧パターン、噴霧粒子を供給する噴霧容器を備えたエアゾール缶、薬剤ボトルを用いることができる。
　また、本発明の抗菌抗カビ組成物は、本発明の効果を奏する限り、液剤に限らず、有効成分である（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分と有機発泡剤を加熱して、有効成分を蒸散させる加熱蒸散剤として用いることもできる。 <Formulation type>
The antibacterial and antifungal composition of the present invention can be used as various formulations. Formulations include, for example, oils, emulsions, wettable powders, flowables (suspensions in water, emulsifiers in water, etc.), microcapsules, powders, granules, tablets, liquids, gels, sol formulations, and piezo formulations. Formulations, air-blown formulations, sprays, aerosols and the like can be mentioned.
Among them, propellants such as spray agents and aerosol agents are preferable in terms of improving not only the amount of adhesion of the antibacterial and antifungal composition of the present invention to an object in a wet environment but also the amount of fixation. Moreover, it is useful as a simple formulation type. In order to prepare a spray or aerosol, an aerosol can having a predetermined spray pattern and a spray container for supplying sprayed particles, or a drug bottle can be used.
In addition, the antibacterial and antifungal composition of the present invention is not limited to a liquid agent as long as the effect of the present invention is exhibited. It can also be used as a heating transpiration agent that transpires the active ingredient.
＜噴霧容器＞
　本発明における噴霧剤を噴霧するための噴霧容器としては、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を含有する抗菌抗カビ組成物を容易に充填でき、噴霧できるものであれば限定されないが、汎用性や使いやすさを考慮すると、以下の３つの噴霧容器が好ましい。
（１）噴霧可能なポンプ式ノズルを装着したディスペンサー式噴霧容器：この噴霧容器は、大気圧で噴霧でき、加圧ガスなどを必要とせず、かつ容器構造も比較的単純であるので安全性が高く、携帯用に向く噴霧容器である。構造は吸い上げ式のチューブを装着した押し出しポンプ式のノズルと、これを固定し内容物を充填するねじ式容器からなる。
（２）トリガー式噴霧容器：この噴霧容器は、内容物を充填する容器本体の口部にピストル状のトリガー式噴霧ディスペンサーが装着されたものであり、大気圧で噴霧でき、噴霧容器として汎用性の高いものである。ここでいうトリガー式噴霧容器には、噴霧機能を高めるために、トリガー式噴霧容器の一部を改良したものも全て含まれる。
（３）エアゾール式噴霧容器：この噴霧容器は、容器内へ噴射剤を充填することによって、上記（１）（２）の２つの噴霧容器では実現できない連続した噴霧を可能とするものである。一般的に、エアゾール式噴霧容器を用いると、上記（１）（２）の２つの噴霧容器に比べ、より細かな霧状に噴霧することが可能となる。
　上記（３）のエアゾール式噴霧容器には、ボタンを押すことにより一度に有効成分を含む内容液の全量を噴射させるエアゾールタイプの製剤である全量噴霧型エアゾールや、定量噴霧用エアゾールバルブを備えたエアゾール容器が含まれている。本発明における噴霧剤は、この定量噴霧型エアゾール容器に本発明の抗菌抗カビ組成物を充填したものが、湿潤環境に存在する対象物への付着量のみならず定着量を向上させる点において好適である。 <Spray container>
As the spray container for spraying the spray agent in the present invention, it is possible to easily fill and spray the antibacterial and antifungal composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component. Although not limited, the following three spray containers are preferable in consideration of versatility and ease of use.
(1) Dispenser-type spray container equipped with a sprayable pump-type nozzle: This spray container can spray at atmospheric pressure, does not require pressurized gas, etc., and has a relatively simple container structure, so it is safe. It is a tall, portable spray container. The structure consists of a push-pump type nozzle fitted with a suction type tube and a screw type container that is fixed and filled with contents.
(2) Trigger-type spray container: This spray container has a pistol-shaped trigger-type spray dispenser attached to the mouth of the container body to be filled with the contents, and can be sprayed at atmospheric pressure, making it versatile as a spray container. is high. The trigger-type spray container referred to here includes all of the trigger-type spray containers partially modified in order to enhance the spray function.
(3) Aerosol type spray container: By filling the container with a propellant, this spray container enables continuous spraying that cannot be achieved with the above two spray containers (1) and (2). In general, the use of an aerosol type spray container enables finer atomization than the above two spray containers (1) and (2).
The aerosol spray container of (3) above is equipped with a total spray type aerosol, which is an aerosol type formulation that sprays the entire amount of the content liquid containing the active ingredient at once by pressing a button, or an aerosol valve for metered spray. Contains an aerosol container. The spraying agent in the present invention is suitable in that the constant amount spray type aerosol container filled with the antibacterial and antifungal composition of the present invention not only improves the amount of adhesion to an object in a wet environment, but also the amount of fixation. is.
＜定量噴霧型エアゾール＞
　定量噴霧型エアゾールとは、１回の噴霧操作で一定量のエアゾール組成物を噴霧するエアゾールである。定量噴霧型エアゾールは、エアゾールバルブに取り付けられた噴霧部材（以下、噴霧ボタンともいう。）が使用者に操作されることにより、エアゾールバルブを通って耐圧容器内のエアゾール組成物（原液と噴射剤）の一定量が噴霧され、原液は噴射剤によって粒子状とされて噴霧粒子として噴霧される。
（定量噴霧用エアゾールバルブ）
　本発明における定量噴霧用エアゾールバルブは、噴霧部材を１回操作することで定量噴霧される定量型のエアゾールバルブであり、その噴霧量は、１回の噴霧操作で０．１～３．０ｍＬの範囲の所定の一定量とされている。１回当たりの噴霧量が０．１～３．０ｍＬの範囲の所定量となるエアゾール組成物を貯留できるハウジングを有する定量噴霧用エアゾールバルブを用いることで、１回の噴霧操作により０．１～３．０ｍＬの範囲の所定の一定量を噴霧することができ、薬剤の噴霧が可能となる。定量噴霧用エアゾールバルブの１回の噴霧操作による噴霧量は、前記範囲であれば所定の噴霧量を適宜設定することができるが、本発明においては０．１～３．０ｍＬの範囲が好ましく、０．５～３．０ｍＬの範囲がより好ましく、０．８～３．０ｍＬの範囲が特に好ましい。また、１回の処理あたりの噴霧回数は、噴霧する空間の広さに応じて適宜調整することができるが、１回の処理あたり１～１０回噴霧が好ましく、１～５回噴霧がさらに好ましく、１～３回噴霧が特に好ましい。 <Fixed amount spray type aerosol>
A metered dose aerosol is an aerosol that sprays a fixed amount of an aerosol composition in one spraying operation. A metered spray type aerosol is a spray member attached to an aerosol valve (hereinafter also referred to as a spray button) that is operated by the user to pass through the aerosol valve and spray the aerosol composition (stock solution and propellant) in a pressure container. ) is sprayed, and the stock solution is granulated with a propellant and sprayed as spray particles.
(Aerosol valve for metered spray)
The fixed quantity spray aerosol valve in the present invention is a fixed quantity type aerosol valve that performs a fixed quantity spray by operating the spray member once, and the spray amount is 0.1 to 3.0 mL in one spray operation. It is assumed to be a predetermined constant amount of range. By using a metered spray aerosol valve having a housing capable of storing an aerosol composition in which the amount of spray per spray is a predetermined amount in the range of 0.1 to 3.0 mL, one spray operation can produce a spray of 0.1 to 0.1 mL. A predetermined constant volume in the range of 3.0 mL can be nebulized, enabling nebulization of the drug. The amount of spray by one spraying operation of the fixed amount spray aerosol valve can be appropriately set to a predetermined spray amount if it is within the above range, but in the present invention, the range of 0.1 to 3.0 mL is preferable. A range of 0.5 to 3.0 mL is more preferred, and a range of 0.8 to 3.0 mL is particularly preferred. In addition, the number of times of spraying per treatment can be appropriately adjusted according to the size of the space to be sprayed. , 1 to 3 sprays are particularly preferred.
（噴霧部材）
　本発明における噴霧部材（噴霧ボタン）は、定量噴霧用エアゾールバルブを介して耐圧容器に取り付けられる部材である。噴霧ボタンには、定量噴霧用エアゾールバルブのステム孔を介して耐圧容器から取り込まれるエアゾール組成物が通過する操作部内通路とエアゾール組成物が噴霧される噴口が形成されている。
　本発明における噴霧ボタンの噴口の内径（噴口孔径）は、噴霧時間を所望の範囲とするという観点から、φ０．４５～３．０ｍｍであることが好ましく、φ０．５～２．０ｍｍがより好ましく、φ０．６～１．６ｍｍがさらに好ましい。また、これらと等しい面積を有する複数の噴口を有していても問題ない。
（噴射圧）
　本発明における定量噴霧型エアゾールは、エアゾール用耐圧容器に原液と噴射剤、すなわちエアゾール組成物が充填され、噴霧ボタンを押圧することにより、１回の押圧によって一定量のエアゾール組成物が噴霧される。噴口から２０ｃｍ離れた位置におけるエアゾール組成物の噴射圧は、５～４０ｇｆであることが好ましく、８～３０ｇｆがより好ましい。噴射圧が前記範囲であることで、噴霧時間を所望の範囲とすることができる。
　なお、前記噴射圧は、２５℃の室温条件下で、定量噴霧型エアゾールの噴口から２０ｃｍの距離を置いたところに横倒しにしたデジタルフォースゲージ（例えば、株式会社イマダ製、型番：ＤＳ２－２Ｎ）に装着した直径φ６０ｍｍの円状の平板の中心に向かってエアゾール組成物を噴霧した際の最大値を噴射荷重とし、平均を算出することにより測定できる。 (Spraying member)
The spray member (spray button) in the present invention is a member that is attached to the pressure container via an aerosol valve for fixed quantity spray. The spray button is formed with a passage in the operating part through which the aerosol composition taken from the pressure container passes through the stem hole of the aerosol valve for fixed quantity spray, and a nozzle hole through which the aerosol composition is sprayed.
In the present invention, the inner diameter of the nozzle of the spray button (orifice diameter) is preferably φ0.45 to 3.0 mm, more preferably φ0.5 to 2.0 mm, from the viewpoint of keeping the spray time within the desired range. , φ0.6 to 1.6 mm are more preferable. Moreover, there is no problem even if there are a plurality of nozzle holes having the same area as these.
(injection pressure)
In the metered spray type aerosol of the present invention, a pressure container for aerosol is filled with a stock solution and a propellant, that is, an aerosol composition, and a spray button is pressed to spray a fixed amount of the aerosol composition with one press. . The injection pressure of the aerosol composition at a position 20 cm away from the nozzle is preferably 5 to 40 gf, more preferably 8 to 30 gf. By setting the injection pressure within the above range, the spray time can be set within the desired range.
The injection pressure was measured at a room temperature of 25° C. with a digital force gauge (for example, manufactured by Imada Co., Ltd., model number: DS2-2N) placed at a distance of 20 cm from the nozzle of the metered aerosol. It can be measured by calculating the average of the maximum value when the aerosol composition is sprayed toward the center of a circular flat plate with a diameter of φ60 mm attached to the device.
（噴霧時間）
　本発明における定量噴霧型エアゾールは、１回の噴霧操作による噴霧時間が１秒以内である。１回当たりの噴霧量が０．１～３．０ｍＬの範囲の所定量であるエアゾール組成物を１秒以内で噴霧させることにより、本発明の抗菌抗カビ組成物に含まれる（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分の拡散性を効率良く高めることができるため、湿潤環境に存在する対象物に対して、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分の付着量のみならず定着量を向上させることができると考えられる。
　１回の噴霧操作による噴霧時間は、０．７５秒以内であることが好ましく、０．０５～０．７５秒がより好ましく、０．１５～０．７５秒がさらに好ましく、０．２０～０．７５秒が特に好ましい。
　本発明において、１回の噴霧操作による噴霧時間を調整する方法としては、例えば、噴霧ボタンの噴口の大きさを調整する方法、定量噴霧型エアゾールの噴射圧を調整する方法、エアゾールバルブのステム孔径を調整する方法、噴射剤の圧力を調整する方法、及びこれらの組み合せ等が挙げられる。
（粒子径）
　本発明における、抗菌抗カビ組成物が噴口から噴霧される時の粒子径については、特に制限はないものの、噴口から５０ｃｍの噴霧距離における平均粒子径が、５μｍ以上１００μｍ未満の範囲であると、湿潤環境に存在する対象物への付着量のみならず定着量を向上させる点において好適である。
　上記粒子径は粒度分布測定容器により測定される数値を意味する。具体的には、粒度分布測定容器のレーザー光発光部より受光部に照射されるレーザービームと、試験検体の噴口との距離が５０ｃｍとなる位置から、噴霧物がレーザービームを垂直に通過するように試験検体を噴霧する。噴霧中に測定を行い、噴霧物の粒度分布を自動演算処理装置により解析することで求めることができる。測定器はマイクロトラック・ベル株式会社製の「ＬＤＳＡ－１４００Ａ」を用いることができる。本発明における粒子径とは５０％体積平均粒子径を意味する。 (Spraying time)
The metered dose aerosol in the present invention has a spraying time of 1 second or less in one spraying operation. By spraying an aerosol composition with a predetermined amount in the range of 0.1 to 3.0 mL per spray within 1 second, (A) oil-soluble contained in the antibacterial antifungal composition of the present invention Since the diffusibility of the antibacterial component and (B) the cationic antibacterial component can be efficiently increased, (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component adhere to the object existing in the moist environment. It is believed that not only the amount but also the fixing amount can be improved.
The spraying time for one spraying operation is preferably within 0.75 seconds, more preferably 0.05 to 0.75 seconds, still more preferably 0.15 to 0.75 seconds, and 0.20 to 0.20 seconds. 0.75 seconds is particularly preferred.
In the present invention, the method of adjusting the spray time by one spray operation includes, for example, a method of adjusting the size of the nozzle of the spray button, a method of adjusting the injection pressure of the metered spray aerosol, and a stem hole diameter of the aerosol valve. , methods of adjusting the pressure of the propellant, and combinations thereof.
(Particle size)
In the present invention, the particle size of the antibacterial and antifungal composition when sprayed from the nozzle is not particularly limited, but if the average particle size at a spray distance of 50 cm from the nozzle is in the range of 5 μm or more and less than 100 μm, This is preferable in terms of improving not only the amount of adhesion to an object in a wet environment but also the amount of fixation.
The particle size means a numerical value measured by a particle size distribution measuring container. Specifically, from a position where the distance between the laser beam emitted from the laser light emitting part of the particle size distribution measurement container to the light receiving part and the injection port of the test sample is 50 cm, the sprayed matter passes through the laser beam perpendicularly. Spray the test sample on the It can be obtained by performing measurement during spraying and analyzing the particle size distribution of the sprayed material with an automatic processor. "LDSA-1400A" manufactured by Microtrac Bell Co., Ltd. can be used as a measuring instrument. The particle size in the present invention means a 50% volume average particle size.
＜本発明の抗菌抗カビ組成物におけるその他の成分＞
　本発明における、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を含有する抗菌抗カビ組成物は、本発明の効果を阻害しない範囲において、消臭成分（フラボノイド類等）などのほか、抗菌性香料成分以外の香料成分等を配合してもよい。また、本発明の抗菌抗カビ組成物を噴霧剤などに製剤化する場合は、通常利用される製剤助剤、例えば、液体担体、界面活性剤、固体担体、凍結防止剤、消泡剤、防腐剤、酸化防止剤、香料成分、帯電防止剤、被膜形成剤及び増粘剤等を配合してもよい。 <Other components in the antibacterial and antifungal composition of the present invention>
In the present invention, the antibacterial and antifungal composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component contains deodorant components (flavonoids, etc.) and the like, as long as the effects of the present invention are not impaired. , a perfume component other than the antibacterial perfume component, etc. may be blended. In addition, when formulating the antibacterial and antifungal composition of the present invention into a spray, etc., commonly used formulation aids such as liquid carriers, surfactants, solid carriers, antifreezing agents, antifoaming agents, antiseptics, etc. agents, antioxidants, perfume ingredients, antistatic agents, film-forming agents, thickeners and the like may be added.
　製剤化する際に使用できる液体担体としては、例えばアルコール類（メタノール、エタノール、イソプロピルアルコール、ブタノール、ヘキサノール、ベンジルアルコール、エチレングリコール等）、エーテル類（ジエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、テトラヒドロフラン、ジオキサン等）、エステル類（酢酸エチル、酢酸ブチル、ミリスチン酸イソプロピル等）、ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等）、芳香族又は脂肪族炭化水素類（キシレン、トルエン、アルキルナフタレン、フェニルキシリルエタン、ケロシン、軽油、ヘキサン、シクロヘキサン等）、ハロゲン化炭化水素類（クロロベンゼン、ジクロロメタン、ジクロロエタン、トリクロロエタン等）、ニトリル類（アセトニトリル、イソブチロニトリル等）、スルホキシド類（ジメチルスルホキシド等）、ヘテロ環系溶剤（スルホラン、γ－ブチロラクトン、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－オクチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン）、酸アミド類（Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等）、炭酸アルキレン類（炭酸プロピレン等）、植物油（大豆油、綿実油等）、植物精油（（Ａ）油溶性抗菌成分には含まれないもの）及び水が挙げられる。水としては、水道水、イオン交換水、蒸留水、ろ過処理した水、滅菌処理した水、地下水等が用いられる。 Examples of liquid carriers that can be used for formulation include alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, etc.), ethers (diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic or aliphatic Hydrocarbons (xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), halogenated hydrocarbons (chlorobenzene, dichloromethane, dichloroethane, trichloroethane, etc.), nitriles (acetonitrile, isobutyro) nitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), heterocyclic solvents (sulfolane, γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-octyl-2-pyrrolidone, 1,3 -dimethyl-2-imidazolidinone), acid amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), alkylene carbonates (propylene carbonate, etc.), vegetable oils (soybean oil, cottonseed oil, etc.), plant essential oils (Those not included in (A) the oil-soluble antibacterial component) and water. As water, tap water, ion-exchanged water, distilled water, filtered water, sterilized water, underground water, and the like are used.
　本発明の抗菌抗カビ組成物は、上記液体担体と併用することにより、（Ｂ）カチオン型抗菌成分が有するヒトに対する目や喉等に対する刺激性を緩和することができる。この刺激緩和効果は、本発明の抗菌抗カビ組成物を噴霧容器に充填して噴霧剤とした際に、顕著に発揮される効果である。この刺激緩和効果の発現のメカニズムは不明であるものの、揮発し難い又は粘性を有する特定の溶剤や精油（成分）などの液体担体との併用により、噴霧粒子が大きくなる傾向にあることに起因するものと、推測される。 By using the antibacterial and antifungal composition of the present invention in combination with the above liquid carrier, it is possible to alleviate the irritation of the cationic antibacterial component (B) to the eyes and throat of humans. This irritation mitigating effect is an effect that is remarkably exhibited when the antibacterial and antifungal composition of the present invention is filled in a spray container to form a spray. Although the mechanism of expression of this stimulation-relieving effect is unknown, it is due to the fact that spray particles tend to become larger when combined with a liquid carrier such as a specific solvent or essential oil (ingredient) that is difficult to volatilize or has viscosity. It is presumed.
　製剤化する際に使用できる界面活性剤としては、非イオン性界面活性剤、陰イオン性界面活性剤及び、両性界面活性剤を用いることができるが、必須成分である（Ｂ）カチオン型抗菌成分の安定性を考慮すると、使用する場合は非イオン性界面活性剤が好ましい。非イオン性界面活性剤としては、例えば、ポリオキシアルキレンアリルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアリルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンアルキルフェニルエーテルホルムアルデヒド縮合物、ポリオキシエチレン－ポリオキシプロピレンブロックポリマー、ポリオキシエチレン－ポリオキシプロピレンブロックポリマーアルキルフェニルエーテル、ソルビタン脂肪酸エステル（ソルビタンモノオレエート、ソルビタンラウレート等）、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリエチレングリコール脂肪酸エステル、ポリエチレングリコール脂肪酸エーテル等が挙げられる。 Nonionic surfactants, anionic surfactants, and amphoteric surfactants can be used as surfactants that can be used for formulation, but the essential component (B) cationic antibacterial component Nonionic surfactants are preferred, if used, due to their stability considerations. Nonionic surfactants include, for example, polyoxyalkylene allylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene allylphenyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene alkylphenyl Ether formaldehyde condensate, polyoxyethylene-polyoxypropylene block polymer, polyoxyethylene-polyoxypropylene block polymer alkylphenyl ether, sorbitan fatty acid ester (sorbitan monooleate, sorbitan laurate, etc.), glycerin fatty acid ester, polyoxyethylene Fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid esters, polyethylene glycol fatty acid ethers and the like can be mentioned.
　本発明における噴霧剤としてエアゾール剤を採用する場合に使用する液体担体としては、飽和炭化水素類又はアルコール類が好ましい。飽和炭化水素類としては、パラフィン系炭化水素類やナフテン系炭化水素類が挙げられるが、中でも、ノルマルパラフィンとイソパラフィンからなるパラフィン系炭化水素類が好ましい。ノルマルパラフィンとしては、炭素数１２～１４が主体のものが代表的で、例えば、中央化成株式会社製のネオチオゾール、ＪＸ日鉱日石エネルギー株式会社製のノルマルパラフィンＮ－１２、ノルマルパラフィンＮ－１３、ノルマルパラフィンＮ－１４、ノルマルパラフィンＭＡ等が、イソパラフィンとしては、例えば、出光興産株式会社製のＩＰクリーンＬＸ、ＩＰソルベント等が挙げられる。アルコール類としては、メタノール、エタノール、イソプロピルアルコール、ブタノール、ヘキサノール、ベンジルアルコール、エチレングリコール等が挙げられる。さらに、液体担体として、脂肪酸エステル類、グリコールエーテル類、ヘテロ環類及びエステル類から選ばれる１種又は２種以上を併用して配合するのが好ましい。
　エアゾール剤に使用される噴射剤としては、公知のものを広く使用することができ、例えば液化石油ガス（ＬＰＧ）、ジメチルエーテル、（ＨＦＯ、ＨＦＣ等の）代替フロン、炭酸ガス、窒素ガス等を挙げることができる。これらの中でもＬＰＧ、ジメチルエーテルを用いるのが好ましい。このエアゾール剤とする場合においては、噴射剤量が全体の３０～９５容量％、特に５０～９５容量％とし、原液（（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分以外に、界面活性剤、液体担体等の総量）が全体の７０～５容量％、特に５０～５容量％とすることができる。 Saturated hydrocarbons or alcohols are preferred as the liquid carrier used when an aerosol agent is employed as the propellant in the present invention. Examples of saturated hydrocarbons include paraffinic hydrocarbons and naphthenic hydrocarbons, among which paraffinic hydrocarbons composed of normal paraffin and isoparaffin are preferred. Typical normal paraffins are mainly composed of 12 to 14 carbon atoms. Normal paraffin N-14, normal paraffin MA and the like, and isoparaffin includes, for example, IP Clean LX and IP Solvent manufactured by Idemitsu Kosan Co., Ltd. Alcohols include methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol and the like. Furthermore, as a liquid carrier, it is preferable to mix one or more selected from fatty acid esters, glycol ethers, heterocycles and esters in combination.
As the propellant used in the aerosol formulation, a wide range of known propellants can be used. be able to. Among these, it is preferable to use LPG and dimethyl ether. In the case of using this aerosol, the amount of propellant is 30 to 95% by volume, particularly 50 to 95% by volume, and the undiluted solution ((A) oil-soluble antibacterial component and (B) cationic antibacterial component) total amount of active agent, liquid carrier, etc.) can be 70-5% by volume, especially 50-5% by volume.
　製剤化する際に使用できる固体担体としては、例えば、粘土類（カオリン、珪藻土、ベントナイト、クレー、酸性白土等）、合成含水酸化珪素、タルク、セラミック、その他の無機鉱物（セリサイト、石英、硫黄、活性炭、炭酸カルシウム、水和シリカ等）、多孔質体等が挙げられる。固体担体の粒子径としては、０．０１μｍ～１５ｍｍの範囲のものが好ましく、中でも０．１μｍ～１０ｍｍの範囲のものがより好ましい。 Solid carriers that can be used for formulation include, for example, clays (kaolin, diatomaceous earth, bentonite, clay, acid clay, etc.), synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (sericite, quartz, sulfur , activated carbon, calcium carbonate, hydrated silica, etc.), porous bodies, and the like. The particle size of the solid carrier is preferably in the range of 0.01 μm to 15 mm, more preferably in the range of 0.1 μm to 10 mm.
　本発明の抗菌抗カビ組成物を用いる空間として、住環境において微生物汚染が問題となる場所、例えば、湿度が高く湿潤な状態が維持されやすい浴室や、頻繁に水が供給される台所シンク・洗面所・トイレなどの水まわり、結露を生じやすい窓や壁を有する部屋などの、屋内の空間が挙げられる。空間の容積は特に限定されないが、床面積が１．０ｍ２以上の空間であれば良い。中でも、０．６～２４畳の部屋に相当する容積（概略２．５～９７．２ｍ３に相当）であることが好ましく、０．７～１２畳の部屋に相当する容積（概略３．０～４８．６ｍ３に相当）であることがより好ましい。また、処理対象物としては、天井、壁、床、浴槽、洗面小物、排水口などが好適に挙げられ、その部材としては、モルタル、ＦＲＰ（繊維強化プラスチック）、アクリル樹脂、ＡＢＳ樹脂（アクリロニトリル－ブタジエン－スチレン共重合合成樹脂）が好適に挙げられる。 Spaces where the antibacterial/antifungal composition of the present invention is used are places where microbial contamination is a problem in the living environment, such as bathrooms where humidity is high and tends to be maintained in a moist state, kitchen sinks and washbasins where water is frequently supplied. Examples include indoor spaces such as rooms with plumbing such as toilets and toilets, and rooms with windows and walls that are prone to condensation. The volume of the space is not particularly limited as long as the space has a floor area of 1.0 m 2 or more. Among them, the volume equivalent to a room of 0.6 to 24 tatami mats (approximately equivalent to 2.5 to 97.2 m 3 ) is preferable, and the volume equivalent to a room of 0.7 to 12 tatami mats (approximately 3.0 ∼48.6 m 3 ). Suitable objects to be treated include ceilings, walls, floors, bathtubs, washcloths, drains, and the like. Butadiene-styrene copolymer synthetic resin) is preferably mentioned.
　以下に実施例によって本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
　なお、実施例において、特に明記しない限り、部は重量部を意味する。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these.
In the examples, parts means parts by weight unless otherwise specified.
＜付着量向上効果確認試験－１＞
（１）試験検体
　下記表１に示す組成で、（Ａ）油溶性抗菌成分、（Ｂ）カチオン型抗菌成分及びエタノールを使用して実施例１、２の試験検体を、（Ａ）油溶性抗菌成分及びエタノールを使用して比較例１の試験検体を、（Ｂ）カチオン型抗菌成分及びエタノールを使用して比較例２の試験検体を調製した。
　（Ａ）油溶性抗菌成分として、４－イソプロピル－３－メチルフェノール（大阪化成株式会社製）を使用し、表１中では「ＩＰＭＰ」と表記した。
　（Ｂ）カチオン型抗菌成分として、塩化ベンザルコニウム（アークサーダジャパン株式会社製）又は１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物（ハイジェニア、タマ化学工業株式会社製）を使用し、表１中では、それぞれ「ＢＺＣ」、「ハイジェニア」と表記した。
　各試験検体の組成を表１に示す。表１中の数値は、重量％を表す。
Figure JPOXMLDOC01-appb-T000004
 <Adhesion amount improvement effect confirmation test-1>
(1) Test specimen The test specimens of Examples 1 and 2 were prepared using (A) an oil-soluble antibacterial component, (B) a cationic antibacterial component and ethanol with the composition shown in Table 1 below, and (A) an oil-soluble antibacterial A test sample of Comparative Example 1 was prepared using the component and ethanol, and a test sample of Comparative Example 2 was prepared using (B) the cationic antimicrobial component and ethanol.
(A) 4-isopropyl-3-methylphenol (manufactured by Osaka Kasei Co., Ltd.) was used as the oil-soluble antibacterial component, and is indicated as "IPMP" in Table 1.
(B) As a cationic antibacterial component, benzalkonium chloride (manufactured by Arksada Japan Co., Ltd.) or 1,4-bis (3,3'-(1-decylpyridinium) methyloxy) butane bromide (Hygenia, Tama Kagaku Kogyo Co., Ltd.) were used, and in Table 1, they were described as "BZC" and "Hygenia", respectively.
The composition of each test sample is shown in Table 1. The numerical values in Table 1 represent % by weight.
Figure JPOXMLDOC01-appb-T000004
（２）試験方法
　上記実施例１、２、比較例１、２の試験検体５２ｖ／ｖ％、精製水４８ｖ／ｖ％となるように試験液を調製した。
　市販の速乾モルタル（３００ｇ）と水（６０ｍＬ）を混合し、バットに薄く広げ、一晩乾燥して得られたモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）を、日本における浴室の壁材を模した試験部材とした。
　実施例１、２、比較例１、２の試験検体から調製した各試験液（１５０ｍＬ）に、試験部材を浸漬して１０分間各試験液を撹拌した。各試験液から取り出した試験部材を、アセトン約１０ｍＬを用いて十分洗浄した。得られたアセトン洗浄液を、４－イソプロピル－３－メチルフェノールは安息香酸アミルを内部標準としてガスクロマトグラフィーにより、塩化ベンザルコニウムは塩化セチルピリジニウムを内部標準として高速液体クロマトグラフィーにより、それぞれ定量分析を行い、試験部材に付着した（Ａ）油溶性抗菌成分である４－イソプロピル－３－メチルフェノールの付着量（ｍｇ）と、（Ｂ）カチオン型抗菌成分である塩化ベンザルコニウムの付着量（ｍｇ）を解析した。
　試験は２回実施した。実施例１、２及び比較例１の試験検体における４－イソプロピル－３－メチルフェノールの付着量（ｍｇ）の平均値及び、実施例１、２の付着量を比較例１の付着量で除した値を「比較例１との比較（倍）」として下記表２に、実施例１及び比較例２の試験検体における塩化ベンザルコニウムの付着量（ｍｇ）の平均値及び、実施例１の付着量を比較例２の付着量で除した値を「比較例２との比較（倍）」として下記表３に示す。 (2) Test method A test solution was prepared so that the test samples of Examples 1 and 2 and Comparative Examples 1 and 2 were 52 v/v% and purified water was 48 v/v%.
Commercially available quick-drying mortar (300 g) and water (60 mL) were mixed, spread thinly on a vat, and dried overnight to obtain a mortar plate (5 cm × 5 cm, about 20 g), which was used to simulate the wall material of a Japanese bathroom. It was used as a test member.
A test member was immersed in each test liquid (150 mL) prepared from the test specimens of Examples 1 and 2 and Comparative Examples 1 and 2, and each test liquid was stirred for 10 minutes. The test member removed from each test solution was thoroughly washed with approximately 10 mL of acetone. The resulting acetone wash solution was quantitatively analyzed by gas chromatography using amyl benzoate as an internal standard for 4-isopropyl-3-methylphenol, and by high-performance liquid chromatography using cetylpyridinium chloride as an internal standard for benzalkonium chloride. and (A) the amount (mg) of 4-isopropyl-3-methylphenol, which is an oil-soluble antibacterial component, and (B) the amount (mg) of benzalkonium chloride, which is a cationic antibacterial component, adhered to the test member. ) was analyzed.
The test was performed in duplicate. The average value of the adhesion amount (mg) of 4-isopropyl-3-methylphenol in the test specimens of Examples 1 and 2 and Comparative Example 1 and the adhesion amount of Examples 1 and 2 were divided by the adhesion amount of Comparative Example 1. Table 2 below shows the values as "comparison (times) with Comparative Example 1", and the average value of the adhesion amount (mg) of benzalkonium chloride in the test specimens of Example 1 and Comparative Example 2, and the adhesion of Example 1 The value obtained by dividing the amount by the adhesion amount of Comparative Example 2 is shown in Table 3 below as "comparison with Comparative Example 2 (times)".
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１、２の試験検体は、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分の付着量が、（Ａ）油溶性抗菌成分のみを含有する比較例１の試験検体に比べて、約１．５倍と約１．９倍に向上することが明らかとなった。
　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分の付着量を向上させ得ることが明らかとなった。
　また、表３に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１の試験検体は、日本における浴室の壁材を模したモルタル板の試験部材への（Ｂ）カチオン型抗菌成分の付着量が、（Ｂ）カチオン型抗菌成分のみを含有する比較例２の試験検体に比べて、約１．４倍に向上することが明らかとなった。
　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ｂ）カチオン型抗菌成分の付着量を向上させ得ることが明らかとなった。
　また、日本における浴室の他の壁材としているＦＲＰ（繊維強化プラスチック）を使用して、同様の付着量向上効果確認試験－１を実施した結果、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分の付着量、（Ｂ）カチオン型抗菌成分の付着量の両方を向上させ得る傾向がみられた。 As shown in Table 2, the test specimens of Examples 1 and 2, which are specific examples of the antibacterial and antifungal composition of the present invention using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, were used in bathrooms in Japan. The adhesion amount of (A) the oil-soluble antibacterial component to the test member of the mortar plate imitating the wall material is about 1.5 compared to the test specimen of Comparative Example 1 containing only the (A) oil-soluble antibacterial component It has been clarified that the efficiency is improved by about 1.9 times.
From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (A) an oil-soluble antibacterial component on the adhesion surface of an antibacterial antifungal composition on an object present in a moist environment It has become clear that the adhesion amount of can be improved.
Further, as shown in Table 3, the test specimen of Example 1, which is a specific example of the antibacterial and antifungal composition of the present invention, which uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, was used in a bathroom in Japan. The amount of the cationic antibacterial component (B) attached to the test member of the mortar plate imitating the wall material is about 1.4 compared to the test specimen of Comparative Example 2 containing only the cationic antibacterial component (B). It was found to double.
From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (B) a cationic antibacterial component on the adhesion surface of an antibacterial antifungal composition of an object present in a moist environment It has become clear that the adhesion amount of can be improved.
In addition, using FRP (fiber reinforced plastic), which is used as another wall material for bathrooms in Japan, a similar adhesion amount improvement effect confirmation test -1 was conducted. There was a tendency that both (A) the adhesion amount of the oil-soluble antibacterial ingredient and (B) the adhesion amount of the cationic antibacterial ingredient could be improved on the adhesion surface of the object.
＜定着量向上効果確認試験－１＞
（１）試験検体
　上記「付着量向上効果確認試験－１」で使用した実施例１、２及び比較例１、２の試験検体を使用した。
　また、上記「付着量向上効果確認試験－１」で調製したものと同じ、日本における浴室の壁材を模したモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）を試験部材として使用した。
（２）試験方法
　上記実施例１、２、比較例１、２の試験検体５２ｖ／ｖ％、精製水４８ｖ／ｖ％となるように試験液を調製した。
　実施例１、２、比較例１、２の試験検体から調製した各試験液（１５０ｍＬ）に、試験部材を浸漬して１０分間各試験液を撹拌した。各試験液から取り出した試験部材を、２００回転／分で撹拌した精製水（３００ｍＬ）中に１秒間浸漬した後、アセトン約１０ｍＬを用いて十分洗浄した。上記「付着量向上効果確認試験－１」と同じ内部標準を使用して、得られたアセトン洗浄液のガスクロマトグラフィー／高速液体クロマトグラフィーによる定量分析を行い、試験部材に付着した（Ａ）油溶性抗菌成分である４－イソプロピル－３－メチルフェノールの定着量（ｍｇ）と、（Ｂ）カチオン型抗菌成分である塩化ベンザルコニウムの定着量（ｍｇ）を解析した。なお、４－イソプロピル－３－メチルフェノールはガスクロマトグラフィーを、塩化ベンザルコニウムは高速液体クロマトグラフィーを用いて分析した。
　試験は２回実施した。実施例１、２及び比較例１の試験検体における４－イソプロピル－３－メチルフェノールの定着量（ｍｇ）の平均値及び、実施例１、２及び比較例１の定着量の平均値を、表２中の実施例１、２及び比較例１の４－イソプロピル－３－メチルフェノールの付着量（ｍｇ）平均値で除した値の百分率（％）を「定着量／付着量（％）」として下記表４に示す。
　また、実施例１及び比較例２の試験検体における塩化ベンザルコニウムの定着量（ｍｇ）の平均値及び、実施例１及び比較例２の定着量の平均値を、表３中の実施例１及び比較例２の塩化ベンザルコニウムの付着量（ｍｇ）平均値で除した値の百分率（％）を「定着量／付着量（％）」として下記表５に示す。 <Fixation amount improvement effect confirmation test-1>
(1) Test Specimen The test specimens of Examples 1 and 2 and Comparative Examples 1 and 2 used in the above-mentioned "adherence amount improvement effect confirmation test-1" were used.
In addition, the same mortar plate (5 cm×5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above-mentioned “deposition amount improvement effect confirmation test-1”, was used as a test member.
(2) Test method A test solution was prepared so that the test samples of Examples 1 and 2 and Comparative Examples 1 and 2 were 52 v/v% and purified water was 48 v/v%.
A test member was immersed in each test liquid (150 mL) prepared from the test specimens of Examples 1 and 2 and Comparative Examples 1 and 2, and each test liquid was stirred for 10 minutes. A test member taken out from each test solution was immersed for 1 second in purified water (300 mL) stirred at 200 rpm, and then thoroughly washed with about 10 mL of acetone. Using the same internal standard as in the above "adhesion amount improvement effect confirmation test-1", the obtained acetone cleaning solution was quantitatively analyzed by gas chromatography / high performance liquid chromatography, and (A) oil-soluble adhering to the test member The fixing amount (mg) of 4-isopropyl-3-methylphenol, which is an antibacterial component, and the fixing amount (mg) of benzalkonium chloride, which is a cationic antibacterial component (B), were analyzed. 4-isopropyl-3-methylphenol was analyzed by gas chromatography, and benzalkonium chloride was analyzed by high performance liquid chromatography.
The test was performed in duplicate. The average value of the amount (mg) of 4-isopropyl-3-methylphenol fixed in the test specimens of Examples 1 and 2 and Comparative Example 1 and the average value of the amount of fixation of Examples 1 and 2 and Comparative Example 1 are shown in the table. The percentage (%) of the value obtained by dividing the average value of the adhesion amount (mg) of 4-isopropyl-3-methylphenol in Examples 1 and 2 and Comparative Example 1 in 2 is defined as "fixed amount/adhesion amount (%)". It is shown in Table 4 below.
In addition, the average value of the fixed amount (mg) of benzalkonium chloride in the test specimens of Example 1 and Comparative Example 2 and the average value of the fixed amount of Example 1 and Comparative Example 2 are shown in Example 1 in Table 3. The percentage (%) of the value obtained by dividing the average value of the adhesion amount (mg) of benzalkonium chloride in Comparative Example 2 is shown in Table 5 below as "fixed amount/adhesion amount (%)".
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表４に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１、２の試験検体の定着量は、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分（ＩＰＭＰ）が、表２に示す（Ａ）油溶性抗菌成分（ＩＰＭＰ）の付着量に対して８７％、８９％と定着性に優れることが明らかとなった一方で、比較例１の試験検体の定着量は、表２に示す付着量に対して６２％程度であることが確認された。すなわち、実施例１と実施例２におけるＩＰＭＰの定着量／付着量（％）は、比較例１におけるＩＰＭＰの定着量／付着量（％）と比べて、どちらも１．４倍であることが明らかとなった。
　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分の定着量を向上させ得るといえる。
　また、表５に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１の試験検体の定着量は、日本における浴室の壁材を模したモルタル板の試験部材への（Ｂ）カチオン型抗菌成分（ＢＺＣ）が、表３に示す（Ｂ）カチオン型抗菌成分（ＢＺＣ）の付着量に対して７６％と定着性に優れることが明らかとなった一方で、比較例２の試験検体の定着量は、表３に示す付着量に対して４０％程度であることが確認された。
　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ｂ）カチオン型抗菌成分の定着量をも向上させ得ることが明らかとなった。
　なお、日本における浴室の他の壁材であるＦＲＰ（繊維強化プラスチック）を使用して、同様の定着量向上効果確認試験－１を実施した結果、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分の定着量、（Ｂ）カチオン型抗菌成分の定着量の両方を向上させ得る傾向がみられた。
　また、（Ａ）油溶性抗菌成分としてリナロール又はメントンを使用し、上記「定着量向上効果確認試験－１」と同様の試験を実施した結果、（Ａ）油溶性抗菌成分であるリナロール又はメントンと、（Ｂ）カチオン型抗菌成分（ＢＺＣ）を併用することにより、湿潤環境に存在する対象物（モルタル／ＦＲＰ）の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分であるリナロール又はメントンの定着量と、（Ｂ）カチオン型抗菌成分（ＢＺＣ）の定着量を、共に向上させ得る傾向がみられた。 As shown in Table 4, the amount of fixation of the test specimens of Examples 1 and 2, which are specific examples of the antibacterial and antifungal composition of the present invention using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, was The (A) oil-soluble antibacterial component (IPMP) on the test member of the mortar board imitating the wall material of a bathroom in Japan is 87% of the amount of (A) oil-soluble antibacterial component (IPMP) shown in Table 2. , 89%, which is excellent in fixing property, while the fixing amount of the test sample of Comparative Example 1 was confirmed to be about 62% of the adhesion amount shown in Table 2. That is, the IPMP fixation amount/adherence amount (%) in Examples 1 and 2 are both 1.4 times the IPMP fixation amount/adhesion amount (%) in Comparative Example 1. It became clear.
From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (A) an oil-soluble antibacterial component on the adhesion surface of an antibacterial antifungal composition on an object present in a moist environment It can be said that the fixing amount of the toner can be improved.
Further, as shown in Table 5, the amount of fixation of the test specimen of Example 1, which is a specific example of the antibacterial and antifungal composition of the present invention, which uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, is The (B) cationic antibacterial component (BZC) on the test member of the mortar board imitating the wall material of a bathroom in Japan is 76% with respect to the adhesion amount of the (B) cationic antibacterial component (BZC) shown in Table 3. On the other hand, it was confirmed that the amount of fixation of the test specimen of Comparative Example 2 was about 40% of the amount of adhesion shown in Table 3.
From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (B) a cationic antibacterial component on the adhesion surface of an antibacterial antifungal composition of an object present in a moist environment It was found that the fixing amount of the toner can also be improved.
In addition, using FRP (fiber reinforced plastic), which is another wall material for bathrooms in Japan, a similar fixation amount improvement effect confirmation test-1 was conducted. There was a tendency that both (A) the amount of fixation of the oil-soluble antibacterial component and (B) the amount of fixation of the cationic antibacterial component could be improved on the adhered surface of the object.
In addition, (A) using linalool or menthone as an oil-soluble antibacterial ingredient, the same test as the above "Fixation amount improvement effect confirmation test-1" was conducted. , (B) By using a cationic antibacterial component (BZC) in combination, (A) Linalool, an oil-soluble antibacterial component, on the adhesion surface of the antibacterial and antifungal composition of the object (mortar / FRP) present in a moist environment Alternatively, there was a tendency that both the fixation amount of menthone and the fixation amount of (B) the cationic antibacterial component (BZC) could be improved.
＜付着量／定着量向上効果確認試験－２＞
（１）試験検体
　上記「付着量向上効果確認試験－１」で使用した実施例１及び比較例１の試験検体を使用した。
　また、上記「付着量向上効果確認試験－１」で調製したものと同じ、日本における浴室の壁材を模したモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）と、ＦＲＰ（繊維強化プラスチック）板（５ｃｍ×５ｃｍ）を、日本における浴室の壁材を模した試験部材として使用した。
（２）試験方法
　上記実施例１、比較例１の試験検体０．５ｍＬと精製水９９９．５ｍＬを混合して試験液を調製した以外は、上記「付着量向上効果確認試験－１」と「定着量向上効果確認試験－１」の試験方法と同様にして試験を実施した。なお、分析機器は高速液体クロマトグラフィー（島津製作所製）を使用した。
　実施例１及び比較例１の試験検体における４－イソプロピル－３－メチルフェノールの付着量（μｇ）の平均値、定着量（μｇ）の平均値及び、実施例１及び比較例１の定着量の平均値を、付着量（μｇ）平均値で除した値の百分率（％）を「定着量／付着量（％）」として下記表６にまとめて示す。 <Adhesion amount/fixing amount improvement effect confirmation test-2>
(1) Test Specimen The test specimens of Example 1 and Comparative Example 1 used in the above-mentioned "adhesion amount improvement effect confirmation test-1" were used.
In addition, the same mortar plate (5 cm × 5 cm, about 20 g) imitating the wall material of a bathroom in Japan and an FRP (fiber reinforced plastic) plate (5 cm × 5 cm) was used as a test member imitating the wall material of a bathroom in Japan.
(2) Test method Except for preparing a test solution by mixing 0.5 mL of the test sample of Example 1 and Comparative Example 1 with 999.5 mL of purified water, the above "Adhesion amount improvement effect confirmation test-1" and " The test was carried out in the same manner as the test method of "Fixation Amount Improvement Effect Confirmation Test-1". A high-performance liquid chromatography (manufactured by Shimadzu Corporation) was used as an analytical instrument.
The average value of the adhesion amount (μg) of 4-isopropyl-3-methylphenol in the test specimens of Example 1 and Comparative Example 1, the average value of the fixing amount (μg), and the fixing amount of Example 1 and Comparative Example 1 The percentage (%) of the value obtained by dividing the average value by the average adhesion amount (μg) is shown in Table 6 below as "fixed amount/adhesion amount (%)".
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表６に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１の試験検体は、日本における浴室の壁材を模したＦＲＰ、モルタルの試験部材への（Ａ）油溶性抗菌成分の付着量が、（Ａ）油溶性抗菌成分のみを含有する比較例１の試験検体に比べて、約１．８倍と約２．７倍に向上することが、さらに、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の付着量に対して８１％、８５％と定着性に優れることが明らかとなった一方で、比較例１の試験検体の定着量は、付着量に対して６０％以下であることが、それぞれ確認された。すなわち、試験部材がＦＲＰとモルタルのどちらであっても、実施例１におけるＩＰＭＰの定着量／付着量（％）は、比較例１におけるＩＰＭＰの定着量／付着量（％）と比べて、１．４倍であることが明らかとなった。　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物の抗菌抗カビ組成物の付着面における、（Ａ）油溶性抗菌成分の付着量、定着量を、日本における浴室の壁材として代表的なモルタルのみならずＦＲＰにおいても向上させ得ることが明らかとなった。 As shown in Table 6, the test specimen of Example 1, which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, was used for the wall of a bathroom in Japan. The amount of (A) oil-soluble antibacterial component adhered to the FRP and mortar test members imitating wood is about 1.8 times that of the test specimen of Comparative Example 1 containing only (A) the oil-soluble antibacterial component. and about 2.7 times higher, and furthermore, (A) It was clarified that the adhesion amount of the oil-soluble antibacterial component (IPMP) is 81% and 85%, which is excellent in fixability, while the comparison It was confirmed that the fixed amount of the test sample of Example 1 was 60% or less of the adhered amount. That is, regardless of whether the test member is FRP or mortar, the fixing amount/adhesion amount (%) of IPMP in Example 1 is 1 .4 times. From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (A) an oil-soluble antibacterial component on the adhesion surface of an antibacterial antifungal composition on an object present in a moist environment It has become clear that the amount of adhesion and the amount of fixation can be improved not only in mortar, which is a typical wall material for bathrooms in Japan, but also in FRP.
＜効力持続実地評価試験＞
（１）試験検体
（試験検体原液の調製）
　下記表７に示す組成で、（Ａ）油溶性抗菌成分であるフェノール化合物、（Ｂ）カチオン型抗菌成分、非晶質二酸化ケイ素及びエタノールを使用して実施例３の試験検体を、フェノール化合物、非晶質二酸化ケイ素及びエタノールを使用して比較例３の試験検体を、カチオン型抗菌成分、非晶質二酸化ケイ素及びエタノールを使用して比較例４の試験検体原液を調製した。
　フェノール化合物として４－イソプロピル－３－メチルフェノール（大阪化成株式会社製）を、カチオン型抗菌成分として塩化ベンザルコニウム（アークサーダジャパン株式会社製）を使用し、表７中では、それぞれ「ＩＰＭＰ」、「ＢＺＣ」と表記した。
　各試験検体原液の組成を表７に示す。表７中の数値は、重量％を表す。
Figure JPOXMLDOC01-appb-T000010
 <On-site evaluation test for duration of efficacy>
(1) Test specimen (preparation of test specimen stock solution)
With the composition shown in Table 7 below, (A) a phenolic compound that is an oil-soluble antimicrobial component, (B) a cationic antimicrobial component, amorphous silicon dioxide, and ethanol were used to prepare the test specimen of Example 3. The phenolic compound, A test sample of Comparative Example 3 was prepared using amorphous silicon dioxide and ethanol, and a test sample stock solution of Comparative Example 4 was prepared using a cationic antibacterial component, amorphous silicon dioxide and ethanol.
4-Isopropyl-3-methylphenol (manufactured by Osaka Kasei Co., Ltd.) was used as the phenol compound, and benzalkonium chloride (manufactured by Arksada Japan Co., Ltd.) was used as the cationic antibacterial component. , "BZC".
Table 7 shows the composition of each test sample stock solution. Numerical values in Table 7 represent % by weight.
Figure JPOXMLDOC01-appb-T000010
（定量噴霧型エアゾール試験検体）
　エアゾール用耐圧缶（容量１３３ｍＬ）に、実施例３、比較例３、４の各試験検体原液を６ｍＬ充填し、エアゾールバルブ（１回噴霧量１ｍＬ、ステム孔（形状：長方形、面積０．７ｍｍ２（１．０ｍｍ×０．７ｍｍ）×２個））でエアゾール用耐圧缶を閉止した。続いて、噴射剤として液化石油ガス（０．４９ＭＰａ（２５℃））を１４ｍＬ加圧充填した。
　エアゾールバルブに噴霧ボタン（噴口孔径φ１ｍｍ×噴口３個）を取り付け、１回当たりの噴霧量が１ｍＬ、４－イソプロピル－３－メチルフェノールの吐出量が、実施例３では３９ｍｇ、比較例３では７８ｍｇ、塩化ベンザルコニウムの吐出量が、実施例３、比較例４共に６ｍｇの、実施例３、比較例３、４の定量噴霧型エアゾール試験検体を得た。
　実施例３、比較例３、４の定量噴霧型エアゾール試験検体の、５０ｃｍの距離からの平均粒子径（Ｄ５０）は、実施例３はＤ５０：２５μｍ、比較例３はＤ５０：２３μｍ、比較例４はＤ５０：２６μｍであった。
　上記平均粒子径（Ｄ５０）は、定量噴霧型エアゾール試験検体の噴口（ノズルの噴口）から噴霧方向（水平方向）に直線で５０ｃｍ離れた位置に、レーザー光回析式粒度測定装置（マイクロトラック・ベル株式会社製「ＬＤＳＡ－１４００Ａ」）を設置し、粒度測定装置に向けて定量噴霧型エアゾール試験検体を、２５℃条件下において噴霧することにより測定した。 (Quantitative spray type aerosol test sample)
A pressure can for aerosol (capacity 133 mL) is filled with 6 mL of each test sample stock solution of Example 3, Comparative Examples 3 and 4, and an aerosol valve (one spray amount 1 mL, stem hole (shape: rectangular, area 0.7 mm 2 (1.0 mm x 0.7 mm) x 2)) to close the aerosol pressure can. Subsequently, 14 mL of liquefied petroleum gas (0.49 MPa (25° C.)) was filled under pressure as a propellant.
A spray button (injection hole diameter φ 1 mm x 3 injection holes) was attached to the aerosol valve, the spray amount per time was 1 mL, and the discharge amount of 4-isopropyl-3-methylphenol was 39 mg in Example 3 and 78 mg in Comparative Example 3. , the discharge amount of benzalkonium chloride was 6 mg in both Example 3 and Comparative Example 4, and quantitative spray type aerosol test specimens of Example 3 and Comparative Examples 3 and 4 were obtained.
The average particle diameter (D50) from a distance of 50 cm of the metered spray type aerosol test specimens of Example 3 and Comparative Examples 3 and 4 was D50: 25 μm for Example 3, D50: 23 μm for Comparative Example 3, and Comparative Example 4. was D50: 26 μm.
The average particle diameter (D50) is measured by a laser beam diffraction particle size measuring device (Microtrac, "LDSA-1400A" manufactured by Bell Co., Ltd.) was installed, and measurement was performed by spraying a metered spray type aerosol test sample toward the particle size analyzer at 25°C.
（２）試験方法
　一般家庭の浴室（１２カ所）において、実施例３の定量噴霧型エアゾール試験検体を噴霧処理する浴室を５カ所、比較例３の定量噴霧型エアゾール試験検体を噴霧処理する浴室を１カ所、比較例４の定量噴霧型エアゾール試験検体を噴霧処理する浴室を４カ所、定量噴霧型エアゾール試験検体を使用しないコントロールの浴室を２カ所として、実地評価試験を実施（２０２１年９月～１１月）した。
　各浴室（１２カ所）の壁や天井等の各部位（面積：１０ｃｍ×１０ｃｍ、２部位）を決定し、ふき取り法にてサンプリングを行い、実地評価試験開始前の１ｃｍ２あたりの黒カビ（主にＣｌａｄｏｓｐｏｒｉｕｍ（真菌）により発生）数を計測し、その平均値を処理前の黒カビ数（数／ｃｍ２）とした。詳しくは、ＢＤラスパーチェック（日本ベクトン・ディッキンソン）を用いてサンプリングを行い、採取液を適宜希釈し、シャーレ上の培地にそれぞれ塗布して黒カビの検出を行った。検出培地としてＰＤＢ（ポテトデキストロース）６ｇ／Ｌに、寒天１５ｇ／Ｌ、細菌の成長を抑えるため抗生物質クロラムフェニコールを１００ｍｇ／Ｌ加えたものを用いた。菌懸濁液を塗布したあと、２５℃のインキュベーターで３～５日間培養後、黒カビ数を計測した。
　各浴室（１２カ所）において、カビ除去剤（カビキラー、ジョンソン株式会社製）を使用して、処理開始時の１ｃｍ２あたりの黒カビ数がゼロとなるように清掃した。
　清掃後、実施例３、比較例３、４の定量噴霧型エアゾール試験検体を、上記所定の浴室において噴霧処理（換気扇をつけたまま、浴室内で１回噴霧する。）して、実地評価試験開始時とした。この実地評価試験開始時から１週間に１回の噴霧処理を８週間継続して、合計９回実施した。
　実地評価試験開始時から４週後と８週後に、上記決定した各浴室（１２カ所）の壁や天井等の２部位において、上記と同じふき取り法にてサンプリングを行い、１ｃｍ２あたりの黒カビ数を計測し、その平均値を４週後、８週後の黒カビ数（数／ｃｍ２）とした。
　実施例３、比較例３、４の定量噴霧型エアゾール試験検体を噴霧処理した浴室における、実地評価試験開始前、実地評価試験開始時、４週後、８週後それぞれの黒カビ数（数／ｃｍ２）の平均値を下記表８にまとめて示す。
　また、実施例３の定量噴霧型エアゾール試験検体を噴霧処理する浴室５カ所のうち、２カ所（浴室Ａ、Ｂ）の実地評価試験開始前と、実地評価試験開始時から８週後の浴室内の写真を図１に示す。 (2) Test method In general household bathrooms (12 locations), there are 5 bathrooms where the metered spray type aerosol test specimen of Example 3 is sprayed, and a bathroom where the metered spray type aerosol test specimen of Comparative Example 3 is sprayed. 1 place, 4 bathrooms where the quantitative spray type aerosol test specimen of Comparative Example 4 is sprayed, and 2 control bathrooms where the quantitative spray type aerosol test specimen is not used. November).
Determine each part (area: 10 cm x 10 cm, 2 parts) such as walls and ceilings of each bathroom (12 places), perform sampling by wiping method, black mold per 1 cm 2 before starting the practical evaluation test (mainly The number of molds generated by Cladosporium (fungi) was counted, and the average value was taken as the number of black mold (number/cm 2 ) before treatment. Specifically, sampling was performed using BD Raspercheck (Nippon Becton Dickinson), the sampled liquid was diluted appropriately, and each was applied to a medium on a petri dish to detect black mold. The detection medium used was 6 g/L PDB (potato dextrose), 15 g/L agar, and 100 mg/L antibiotic chloramphenicol to suppress bacterial growth. After applying the bacterial suspension, the cells were cultured in an incubator at 25° C. for 3 to 5 days, and then the number of black mold was counted.
Each bathroom (12 locations) was cleaned using a mold remover (Kabikiller, manufactured by Johnson, Inc.) so that the number of black mold per 1 cm 2 at the start of treatment was zero.
After cleaning, the quantitative spray type aerosol test specimens of Example 3 and Comparative Examples 3 and 4 are sprayed in the predetermined bathroom (sprayed once in the bathroom with the ventilation fan on) and subjected to a field evaluation test. It's time to start. From the start of this practical evaluation test, the spray treatment was continued once a week for 8 weeks, and was carried out a total of 9 times.
After 4 weeks and 8 weeks from the start of the field evaluation test, the two parts of the walls and ceilings of each bathroom (12 places) determined above were sampled using the same wiping method as above, and the number of black molds per 1 cm 2 was measured, and the average value was taken as the black mold number (number/cm 2 ) after 4 weeks and 8 weeks.
The number of black mold (number/cm 2 ) are summarized in Table 8 below.
In addition, of the five bathrooms where the quantitative spray type aerosol test specimen of Example 3 is sprayed, two locations (bathrooms A and B) before the start of the field evaluation test and eight weeks after the start of the field evaluation test is shown in Fig. 1.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表８に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例３の定量噴霧型エアゾール試験検体は、１週間に１回の噴霧処理を継続することにより、実地評価試験開始時から８週後も黒カビ数がゼロである清掃後の状態を維持することが確認された。
　また、図１の実施例３の定量噴霧型エアゾール試験検体を噴霧処理した浴室Ａ、Ｂの写真に示すとおり、実地評価試験開始前に黒カビが発生していた同じ部位（図１の四角枠内）において、実地評価試験開始時から８週後でも黒カビは全く発生していない状態が維持されることが確認された。さらに、浴室Ｂにおいては、実地評価試験開始前にピンク色のヌメリ（主にＲｈｏｄｏｔｏｒｕｌａ属（酵母）若しくは、Ｍｅｔｈｙｌｏｂａｃｔｅｒｉｕｍ属（細菌）によって発生）が発生していた同じ部位（図１の丸枠内）において、実地評価試験開始時から８週後でもピンクヌメリは全く発生していない状態が維持されることも確認された。
　一方、有効成分が（Ａ）油溶性抗菌成分のみである比較例３の定量噴霧型エアゾール試験検体は、実施例３の定量噴霧型エアゾール試験検体中の油溶性抗菌成分が２倍含有するものであるにもかかわらず、実地評価試験開始時から４週後には黒カビが発生することが明らかとなった。
　また、有効成分が（Ｂ）カチオン型抗菌成分のみである比較例４の定量噴霧型エアゾール試験検体も比較例３の定量噴霧型エアゾール試験検体と同様に、実地評価試験開始時から４週後には黒カビが発生してしまうことが明らかとなった。
　単位面積（１ｃｍ２）当たりの黒カビ数が１個以上の状態は、黒カビの発生を完全には抑制できておらず、いずれ目視で黒カビを確認できる状況となることを意味する。すなわち、単位面積（１ｃｍ２）当たりの黒カビ数ゼロの状態を、長期間にわたり維持することが、浴室などの湿潤環境における微生物汚染の防除には極めて重要なポイントである。 As shown in Table 8, the quantitative spray type aerosol test specimen of Example 3, which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component, was 1 By continuing the spraying treatment once a week, it was confirmed that the post-cleaning state of zero black mold was maintained even after eight weeks from the start of the field evaluation test.
In addition, as shown in the photographs of bathrooms A and B sprayed with the quantitative spray type aerosol test specimen of Example 3 in FIG. ), it was confirmed that even after 8 weeks from the start of the field evaluation test, a state in which no black mold was generated was maintained. Furthermore, in bathroom B, the same site where pink slime (mainly caused by Rhodotorula genus (yeast) or Methylobacterium genus (bacteria)) occurred before the start of the field evaluation test (circled in FIG. 1) , it was also confirmed that pink slime did not occur at all even after 8 weeks from the start of the field evaluation test.
On the other hand, the quantitative spray type aerosol test specimen of Comparative Example 3, in which the active ingredient is (A) only the oil-soluble antibacterial component, contains twice the oil-soluble antibacterial component in the quantitative spray type aerosol test specimen of Example 3. In spite of this, it became clear that black mold was generated 4 weeks after the start of the field evaluation test.
In addition, the quantitative spray type aerosol test specimen of Comparative Example 4, in which the active ingredient is only the cationic antibacterial component (B), is the same as the quantitative spray type aerosol test specimen of Comparative Example 3. Four weeks after the start of the practical evaluation test, It became clear that black mold would occur.
A state in which the number of black molds per unit area (1 cm 2 ) is 1 or more means that the occurrence of black molds cannot be completely suppressed, and black molds will eventually be visually confirmed. In other words, it is extremely important to maintain a state of zero black mold per unit area (1 cm 2 ) for a long period of time for the prevention of microbial contamination in wet environments such as bathrooms.
＜浴室空間における付着量／定着量向上効果確認試験＞
（１）試験検体
（試験検体原液の調製）
　上記「付着量向上効果確認試験－１」の実施例１と比較例１の試験検体を、試験検体原液とした。
　エアゾール用耐圧缶（容量１３３ｍＬ）に、実施例１、比較例１の各試験検体原液を６ｍＬ充填し、エアゾールバルブ（１回噴霧量１ｍＬ、ステム孔（形状：長方形、面積０．７ｍｍ２（１．０ｍｍ×０．７ｍｍ）×２個））でエアゾール用耐圧缶を閉止した。続いて、噴射剤として液化石油ガス（０．４９ＭＰａ（２５℃））を１４ｍＬ加圧充填した。
　エアゾールバルブに噴霧ボタン（噴口孔径φ１ｍｍ×噴口３個）を取り付け、１回噴霧当たりの噴霧量が１ｍＬ、４－イソプロピル－３－メチルフェノールの吐出量が３９ｍｇ、塩化ベンザルコニウムの吐出量が６ｍｇである実施例１、比較例１の定量噴霧型エアゾール試験検体を得た。 <Confirmation test for effect of improving adhesion amount/fixing amount in bathroom space>
(1) Test specimen (preparation of test specimen stock solution)
The test specimens of Example 1 and Comparative Example 1 of the above-mentioned "adhesion amount improvement effect confirmation test-1" were used as the test specimen undiluted solutions.
A pressure can for aerosol (capacity 133 mL) is filled with 6 mL of each test sample stock solution of Example 1 and Comparative Example 1, and an aerosol valve (one spray amount 1 mL, stem hole (shape: rectangular, area 0.7 mm 2 (1 0 mm x 0.7 mm) x 2)) to close the aerosol pressure can. Subsequently, 14 mL of liquefied petroleum gas (0.49 MPa (25° C.)) was filled under pressure as a propellant.
A spray button (hole diameter φ1 mm x 3 nozzles) is attached to the aerosol valve, the spray amount per spray is 1 mL, the discharge amount of 4-isopropyl-3-methylphenol is 39 mg, and the discharge amount of benzalkonium chloride is 6 mg. Quantitative spray type aerosol test specimens of Example 1 and Comparative Example 1 were obtained.
（２）試験方法
　上記「付着量向上効果確認試験－１」で調製したものと同じ、日本における浴室の壁材を模したモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）を試験部材として、浴室（１．８ｍ×１．８ｍ×高さ２ｍ）の天井、側壁の２カ所に、それぞれ１０個の試験部材（合計２０個）を貼り付けた。
　浴室内（２５℃）の湿度を９０％以上に調湿し、２カ所の試験部材２０個に水をかけて十分に濡らした状態とした後に、実施例１、比較例１の定量噴霧型エアゾール試験検体を、各浴室の入口から浴室中央に向かって噴霧処理（１回噴霧）し、噴霧処理から３０分後に天井の試験部材を２個、側壁の試験部材を２個それぞれ回収し、付着量評価用の試験部材（合計４個）とした。
　上記付着量評価用の試験部材（合計４個）を回収後、残りの試験部材（１６個）にシャワー（流量３０ｍＬ／秒）を１秒間直接かけ、天井の試験部材を２個、側壁の試験部材を２個それぞれ回収し、試験開始日の定着量評価用の試験部材（合計４個）とした。
　さらに経時的な影響を評価するために、残りの天井の試験部材２個、側壁の試験部材２個それぞれを浴室内で１日間放置し、再度シャワー（流量３０ｍＬ／秒）を１秒間直接かける操作を行い、試験開始後１日の定着量評価用の試験部材（合計４個）とした。その後、２４時間毎に残りの試験部材にシャワー（流量３０ｍＬ／秒）を１秒間直接かける操作を続け、試験開始後５日の定着量評価用の試験部材（合計４個）と、試験開始後７日の定着量評価用の試験部材（合計４個）とした。
　回収した各試験部材は回収後速やかに、アセトン約１０ｍＬを用いて十分洗浄した。上記「付着量向上効果確認試験－１」と同じ内部標準を使用して、得られたアセトン洗浄液のガスクロマトグラフィーによる定量分析を行い、試験部材に付着した（Ａ）油溶性抗菌成分である４－イソプロピル－３－メチルフェノールの付着量と定着量（μｇ）を解析した。
　付着量評価用の試験部材（天井２個、側壁２個）の成分（Ａ）の付着量（μｇ）の平均値、試験開始日及び試験開始後１日の定着量評価用の試験部材（各天井２個、各側壁２個）の成分（Ａ）の定着量（μｇ）の平均値それぞれを、実施例１、比較例１の定量噴霧型エアゾール試験検体の結果として、それぞれ下記表９、１０に示す。また、試験開始日又は試験開始後１日、５日、７日の定着量評価用の試験部材における成分（Ａ）の平均定着量（μｇ）を、付着量評価用の試験部材における成分（Ａ）の平均付着量（μｇ）で除した値の百分率（％）を「定着量／付着量（％）」として、それぞれ下記表９、１０にまとめて示す。 (2) Test method The same mortar plate (5 cm x 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above "Deposited amount improvement effect confirmation test-1", was used as a test member. Ten test members (a total of 20 pieces) were affixed to each of two locations on a ceiling and a side wall measuring .8m x 1.8m x height 2m.
The humidity in the bathroom (25 ° C.) was adjusted to 90% or more, and 20 test members at two locations were sufficiently wetted with water. The test specimen is sprayed (once sprayed) from the entrance of each bathroom toward the center of the bathroom, and 30 minutes after the spray treatment, two test members on the ceiling and two test members on the side walls are collected. It was set as the test member (a total of 4 pieces) for evaluation.
After collecting the test members (4 in total) for evaluating the amount of adhesion, the remaining test members (16) are directly showered (flow rate 30 mL / sec) for 1 second, 2 ceiling test members, side wall test Two members were collected and used as test members (four in total) for fixing amount evaluation on the test start date.
In order to further evaluate the effects over time, the remaining 2 test members for the ceiling and 2 test members for the side walls were left in the bathroom for 1 day, and then showered again (flow rate 30 mL/sec) directly for 1 second. and used as test members (four pieces in total) for evaluating the amount of fixation one day after the start of the test. After that, the operation of directly applying a shower (flow rate of 30 mL / sec) to the remaining test members for 1 second every 24 hours was continued. It was used as a test member (total of 4 pieces) for evaluating the amount of fixation after 7 days.
Immediately after recovery, each recovered test member was thoroughly washed with about 10 mL of acetone. Using the same internal standard as in the above "adhesion amount improvement effect confirmation test-1", the obtained acetone cleaning solution was quantitatively analyzed by gas chromatography, and (A) oil-soluble antibacterial component 4 adhered to the test member. -Isopropyl-3-methylphenol adhesion amount and fixing amount (μg) were analyzed.
Average value of adhesion amount (μg) of component (A) on test members for adhesion amount evaluation (2 ceilings, 2 side walls), test member for adhesion amount evaluation on the day of test start and one day after test start (each The average values of the fixed amount (μg) of the component (A) on the ceiling (2 ceilings, 2 on each side wall) are shown in Tables 9 and 10 below, respectively, as the results of the quantitative spray type aerosol test specimens of Example 1 and Comparative Example 1. shown in In addition, the average amount of fixation (μg) of the component (A) in the test member for evaluating the amount of fixation on the day of the start of the test or 1 day, 5 days, and 7 days after the start of the test was calculated as the component (A ) divided by the average adhesion amount (μg) is shown in Tables 9 and 10 below as "fixed amount/adhesion amount (%)".
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表９、１０に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例１の定量噴霧型エアゾール試験検体は、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分（ＩＰＭＰ）の付着量が、（Ａ）油溶性抗菌成分のみを含有する比較例１の定量噴霧型エアゾール試験検体に比べて、天井では１．２５倍（９．０÷７．２＝１．２５）、側壁では１．２９倍（７．２÷５．６≒１．２９）と向上することが確認された。
　また、試験開始日及び試験開始後１日では、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する実施例１の定量噴霧型エアゾール試験検体は、モルタル板の試験部材への（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着量が、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の付着量に対して７２％～９７％と定着性に優れることが確認された一方で、比較例１の定量噴霧型エアゾール試験検体の定着量は、付着量に対して４８％～７９％程度と定着性が良くないことが確認された。より詳細に説明すると、試験開始日及び試験開始後１日では、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着量が、天井では、実施例１が８２％、７５％に対して比較例１が７５％、５８％であり、側壁では実施例１が９７％、７２％に対して比較例１が７９％、４８％であり、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着性に大きな差があることが確認された。
　さらに、試験開始後５日、７日では、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着量が、天井では、実施例１が３９％、１５％に対して比較例１が３２％、８％であり、側壁では実施例１が２９％、１６％に対して比較例１が２１％、９％と、噴霧処理から５日及び７日経過後においても、（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着性に大きな差があることも確認された。
　これらの結果から、試験開始日から試験開始後７日まで、実施例１の（Ａ）油溶性抗菌成分（ＩＰＭＰ）の定着量／付着量（％）の値は、対応する比較例１の（Ａ）油溶性抗菌成分（ＩＰＭＰ）定着量／付着量（％）と比べて１．１～１．９倍となり、７日にわたって定着性に優れるものであることが明らかとなった。
　この結果より、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用することにより、実用場面においても、湿潤環境に存在する対象物の噴霧粒子付着面における、（Ａ）油溶性抗菌成分の付着量、定着量ともに向上させ得ると考えられる。 As shown in Tables 9 and 10, the quantitative spray type aerosol test specimen of Example 1, which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, , The amount of (A) the oil-soluble antibacterial component (IPMP) adhered to the test member of the mortar board imitating the wall material of a Japanese bathroom is (A) the fixed amount spray type of Comparative Example 1 containing only the oil-soluble antibacterial component 1.25 times (9.0 ÷ 7.2 = 1.25) on the ceiling and 1.29 times (7.2 ÷ 5.6 ≒ 1.29) on the side wall compared to the aerosol test sample was confirmed.
In addition, on the test start date and one day after the start of the test, the fixed amount spray type aerosol test specimen of Example 1 using both (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component was applied to the test member of the mortar board. (A) The amount of fixation of the oil-soluble antibacterial component (IPMP) was confirmed to be 72% to 97% of the amount of adhesion of the (A) oil-soluble antibacterial component (IPMP). It was confirmed that the fixation amount of the metered spray type aerosol test sample of Example 1 was about 48% to 79% of the adhesion amount, indicating that the fixability was not good. More specifically, on the test start date and one day after the test start, (A) the amount of fixing of the oil-soluble antibacterial component (IPMP) on the ceiling was 82% in Example 1 and 75% in Comparative Example 1. are 75% and 58%, and on the side wall, Example 1 is 97% and 72%, while Comparative Example 1 is 79% and 48%, and (A) the fixability of the oil-soluble antibacterial component (IPMP) is large. A difference was confirmed.
Furthermore, on the 5th and 7th days after the start of the test, the amount of (A) oil-soluble antibacterial component (IPMP) fixed on the ceiling was 39% and 15% in Example 1, and 32% and 8% in Comparative Example 1. %, and on the side wall, Example 1 was 29%, 16%, Comparative Example 1 was 21%, 9%, and even after 5 days and 7 days from the spraying treatment, (A) oil-soluble antibacterial component (IPMP ) was also confirmed to have a large difference in fixability.
From these results, from the start date of the test to 7 days after the start of the test, the value of the fixing amount / adhesion amount (%) of (A) the oil-soluble antibacterial component (IPMP) of Example 1 is the corresponding value of Comparative Example 1 ( A) 1.1 to 1.9 times the oil-soluble antibacterial component (IPMP) fixation amount/adhesion amount (%), demonstrating excellent fixability over 7 days.
From this result, by using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, even in a practical situation, (A) oil-soluble antibacterial It is believed that both the attachment amount and fixing amount of the component can be improved.
＜付着量／定着量向上効果確認試験－３＞
（１）試験検体
（Ｂ）カチオン型抗菌成分１重量部に対して、（Ａ）油溶性抗菌成分を０．００１～２０重量部とした、下記の試験検体を作製した。
　下記表１１に示す、（Ａ）油溶性抗菌成分が１３ｗ／ｖ％となるようにエタノールで希釈し、これを５２ｖ／ｖ％、精製水４８ｖ／ｖ％となるように希釈した。この希釈液を遠心分離（３５００ｒｐｍ、１２分）し、水層部分に、下記表１１に示す（Ｂ）カチオン型抗菌成分である塩化ベンザルコニウム又は１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物を２ｗ／ｖ％となるように添加して、実施例試験検体ａ～ｆとした。また、（Ａ）として４－イソプロピル－３－メチルフェノールを「ＩＰＭＰ」を使用した上記水層部分に、（Ｂ）カチオン型抗菌成分を添加しないもの、すなわち、「ＩＰＭＰ」のエタノール水溶液を比較例試験検体ａとした。 <Adhesion amount/fixing amount improvement effect confirmation test-3>
(1) Test specimens The following test specimens were prepared by adding 0.001 to 20 parts by weight of the oil-soluble antibacterial component (A) to 1 part by weight of the cationic antibacterial component (B).
The oil-soluble antibacterial component (A) shown in Table 11 below was diluted with ethanol to 13 w/v%, and diluted to 52 v/v% and purified water to 48 v/v%. This diluted solution was centrifuged (3500 rpm, 12 minutes), and the water layer part was added with (B) cationic antimicrobial component benzalkonium chloride or 1,4-bis(3,3'-(B) shown in Table 11 below. 1-decylpyridinium)methyloxy)butane bromide was added to 2 w/v% to obtain example test specimens af. In addition, (A) 4-isopropyl-3-methylphenol "IPMP" was used as the above water layer part, and (B) no cationic antibacterial component was added, that is, "IPMP" ethanol aqueous solution was used as a comparative example. It was designated as test specimen a.
（２）付着量向上効果確認試験
　市販の速乾モルタル（３００ｇ）と水（６０ｍＬ）を混合し、バットに薄く広げ、一晩乾燥して得られたモルタル板（２ｃｍ×２ｃｍ、約３ｇ）を、日本における浴室の壁材を模した試験部材とした。
　実施例試験検体ａ～ｆ又は比較例試験検体ａそれぞれ（１０ｍＬ）に、試験部材を浸漬して１０回転倒混和を行った。各試験検体から取り出した試験部材を、アセトン約５ｍＬを用いて十分洗浄した。得られたアセトン洗浄液に、内部標準としてフタル酸ジブチルを加えて、ガスクロマトグラフィーにより定量分析を行い、試験部材に付着した（Ａ）油溶性抗菌成分の付着量（ｍｇ）を解析した。
　各実施例試験検体ａ～ｆ又は比較例試験検体ａの組成と、試験部材に付着した（Ａ）油溶性抗菌成分の付着量を「付着量（ｍｇ／試験片）」として、下記表１１にまとめて示す。
　表１１中では、４－イソプロピル－３－メチルフェノールを「ＩＰＭＰ」、塩化ベンザルコニウムを「ＢＺＣ」、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物を「ハイジェニア」と表記した。 (2) Adhesion amount improvement effect confirmation test Commercially available quick-drying mortar (300 g) and water (60 mL) are mixed, spread thinly on a vat, and dried overnight to obtain a mortar plate (2 cm × 2 cm, about 3 g). , was used as a test member imitating the wall material of the bathroom in Japan.
A test member was immersed in each of Example test samples a to f or Comparative example test sample a (10 mL) and mixed by inversion 10 times. The test member from each test specimen was thoroughly washed with approximately 5 mL of acetone. Dibutyl phthalate was added as an internal standard to the obtained acetone cleaning solution, and quantitative analysis was performed by gas chromatography to analyze the amount (mg) of the (A) oil-soluble antibacterial component adhering to the test member.
The composition of each example test specimen a to f or comparative example test specimen a and the adhesion amount of (A) oil-soluble antibacterial component adhered to the test member are shown in Table 11 below as "adhesion amount (mg / test piece)". Shown together.
In Table 11, 4-isopropyl-3-methylphenol is "IPMP", benzalkonium chloride is "BZC", 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane bromide Described as "hygenia".
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表１１に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例試験検体ａは、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分の付着量が、（Ａ）油溶性抗菌成分のみを含有する比較例試験検体ａに比べて、約１．５倍に向上することが明らかとなった。本試験においても、上記表２に示す結果と同様に、（Ａ）油溶性抗菌成分と（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物に対する（Ａ）油溶性抗菌成分の付着量が大きく向上する効果が得られることが確認された。 As shown in Table 11, the example test specimen a, which is a specific example of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, is a bathroom wall material in Japan. The amount of (A) the oil-soluble antibacterial component attached to the test member of the mortar plate imitating the (A) compared to the comparative example test specimen a containing only the oil-soluble antibacterial component is improved by about 1.5 times. It became clear. In this test, similar to the results shown in Table 2 above, (A) the oil-soluble antibacterial component and (B) the cationic antibacterial component were used in combination to suppress (A) the oil-soluble antibacterial component against objects present in a moist environment. It was confirmed that the effect of greatly improving the amount of the component attached was obtained.
（３）定着量向上効果確認試験
　実施例試験検体ａ～ｆ又は比較例試験検体ａそれぞれ（１０ｍＬ）に、試験部材を浸漬して１０回転倒混和を行った。各試験検体から取り出した試験部材を、２００回転／分で撹拌した精製水（５０ｍＬ）中に１秒間浸漬し、アセトン約５ｍＬを用いて十分洗浄した。得られたアセトン洗浄液に、内部標準としてフタル酸ジブチルを加えて、ガスクロマトグラフィーにより定量分析を行い、試験部材に付着した（Ａ）油溶性抗菌成分の定着量（ｍｇ）を解析した。
　実施例試験検体ａ～ｆにおける、（Ａ）油溶性抗菌成分の定着量を「定着量（ｍｇ／試験片）」、この定着量を、上記表１１に示す付着量で除した値の百分率（％）を「定着量／付着量（％）」として、下記表１２にまとめて示す。 (3) Fixing Amount Improvement Effect Confirmation Test A test member was immersed in each (10 mL) of the test samples a to f of the examples and the test sample a of the comparative example, and mixed by inversion 10 times. A test member taken out from each test specimen was immersed for 1 second in purified water (50 mL) stirred at 200 rpm, and thoroughly washed with about 5 mL of acetone. Dibutyl phthalate was added as an internal standard to the obtained acetone cleaning solution, and quantitative analysis was performed by gas chromatography to analyze the amount (mg) of the (A) oil-soluble antibacterial component adhered to the test member.
In Example test specimens a to f, the amount of (A) fixed amount of oil-soluble antibacterial component is "fixed amount (mg/test piece)", and the percentage of the value obtained by dividing this fixed amount by the adhesion amount shown in Table 11 above ( %) is collectively shown in Table 12 below as "fixed amount/deposited amount (%)".
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表１２に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例試験検体ａ～ｆは、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分が、表１０に示す（Ａ）油溶性抗菌成分（ＩＰＭＰ）の付着量に対して６５～９７％であり、良好な定着性を示すものであることが明らかとなった。すなわち、本発明における（Ａ）油溶性抗菌成分は、フェノール化合物のみならず、抗菌性香料成分を採用した場合においても、湿潤環境に存在する対象物に対する優れた定着性を実現できることが確認された。また、（Ａ）油溶性抗菌成分として抗菌性香料成分である、酢酸リナリル、メントール、１，８－シネオール、メントン、リナロール、酢酸メンチルの何れも、（Ｂ）カチオン型抗菌成分と併用することにより、湿潤環境に存在する対象物への定着性に優れる傾向があった。 As shown in Table 12, example test specimens a to f, which are specific examples of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, are used in bathrooms in Japan. The (A) oil-soluble antibacterial component on the test member of the mortar plate imitating the wall material was 65 to 97% of the adhesion amount of the (A) oil-soluble antibacterial component (IPMP) shown in Table 10, and it was good. It became clear that it is what shows fixability. That is, it was confirmed that the oil-soluble antibacterial component (A) in the present invention can realize excellent fixability to objects existing in a wet environment not only when a phenol compound but also when an antibacterial fragrance component is used. . In addition, any of linalyl acetate, menthol, 1,8-cineole, menthone, linalool, and menthyl acetate, which are antibacterial fragrance ingredients as (A) oil-soluble antibacterial ingredients, can be used in combination with (B) cationic antibacterial ingredients. , tended to be excellent in fixability to objects existing in a wet environment.
＜付着量／定着量向上効果確認試験－４＞
（１）試験検体
　「付着量／定着量向上効果確認試験－３」で用いた、実施例試験検体ｃ、ｄ、ｅ、ｆを使用した。また、実施例試験検体ｄのボルネオールをリナロール、１，８－シネオールに代えた試験検体を実施例試験検体ｇ、ｊに、実施例試験検体ｂのＩＰＭＰをゲラニオール、カンファーに代えた試験検体を実施例試験検体ｈ、ｉに、実施例試験検体ｃの「ＢＺＣ」を塩化セチルピリジニウムに代えた試験検体を実施例試験検体ｋとした。また、比較例試験検体ａの「ＩＰＭＰ」を、ボルネオール、シトロネラール、リナロール、ゲラニオール、カンファー、１，８－シネオールそれぞれに代えた試験検体を、比較例試験検体ｂ、ｃ、ｄ、ｅ、ｆ、ｇとした。
（２）付着量向上効果確認試験
　上記「付着量向上効果確認試験－１」で調製したものと同じ、日本における浴室の壁材を模したモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）を試験部材として使用し、実施例試験検体ｃ～ｋ又は比較例試験検体ｂ～ｇそれぞれ（１５０ｍＬ）に、試験部材を浸漬して１０分間各試験液を撹拌することと、洗浄用のアセトン約１０ｍＬ使用する以外は、上記「付着量／定着量向上効果確認試験－３」の「（２）付着量向上効果確認試験」と同様に試験を行った。
（３）定着量向上効果確認試験
　上記「付着量向上効果確認試験－１」で調製したものと同じ、日本における浴室の壁材を模したモルタル板（５ｃｍ×５ｃｍ、約２０ｇ）を試験部材として使用し、実施例試験検体ｃ～ｋ又は比較例試験検体ｂ～ｇそれぞれ（１５０ｍＬ）に、試験部材を浸漬して１０分間各試験液を撹拌した。各試験液から取り出した試験部材を、２００回／分で攪拌した精製水（３００ｍＬ）中に１秒間浸漬した後、アセトン約１０ｍＬを用いて十分洗浄した。その後の定量分析は、上記「付着量／定着量向上効果確認試験－３」の「（３）定着量向上効果確認試験」と同様に試験を行った。
　各実施例試験検体ｃ～ｋ又は比較例試験検体ｂ～ｇの組成と、試験部材に付着した（Ａ）油溶性抗菌成分の付着量を「付着量（ｍｇ／試験片）」、定着量を「定着量（ｍｇ／試験片）」、この定着量を付着量で除した値の百分率（％）を「定着量／付着量（％）」として、下記表１３にまとめて示す。
　表１３では、塩化ベンザルコニウムを「ＢＺＣ」、１，４－ビス（３，３’－（１－デシルピリジニウム）メチルオキシ）ブタン臭化物を「ハイジェニア」、塩化セチルピリジニウムを「ＣＰＣ」と表記した。 <Adhesion amount/fixing amount improvement effect confirmation test-4>
(1) Test Specimens Example test specimens c, d, e, and f used in the “adhesion amount/fixation amount improvement effect confirmation test-3” were used. In addition, test specimens in which borneol in example test specimen d was replaced with linalool and 1,8-cineol were used in example test specimens g and j, and IPMP in example test specimen b was replaced with geraniol and camphor. Example test sample k was obtained by replacing “BZC” of example test sample c with cetylpyridinium chloride in example test samples h and i. In addition, the test samples obtained by replacing “IPMP” of Comparative Example Test Specimen a with borneol, citronellal, linalool, geraniol, camphor, and 1,8-cineole were prepared as Comparative Example Test Specimens b, c, d, e, f, g.
(2) Adhesion amount improvement effect confirmation test The same mortar plate (5 cm × 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above "Adhesion amount improvement effect confirmation test-1", was used as a test member. Use, except that the test member is immersed in each (150 mL) of example test samples c to k or comparative example test samples b to g (150 mL) and each test solution is stirred for 10 minutes, and about 10 mL of acetone for washing is used. was conducted in the same manner as in "(2) Adhesion amount improvement effect confirmation test" of the above "Adhesion amount/fixing amount improvement effect confirmation test-3".
(3) Fixing amount improvement effect confirmation test The same mortar plate (5 cm × 5 cm, about 20 g) imitating the wall material of a bathroom in Japan, which was prepared in the above “Adhesion amount improvement effect confirmation test-1”, was used as a test member. A test member was immersed in each (150 mL) of test samples c to k of Examples or test samples b to g of Comparative Examples, and each test solution was stirred for 10 minutes. A test member taken out from each test solution was immersed for 1 second in purified water (300 mL) stirred at 200 times/min, and then thoroughly washed with about 10 mL of acetone. The subsequent quantitative analysis was performed in the same manner as in "(3) Fixing amount improvement effect confirmation test" of the above "Adhesion amount/fixing amount improvement effect confirmation test-3".
The composition of each example test specimen c to k or comparative example test specimen b to g, and the adhesion amount of (A) oil-soluble antibacterial component adhered to the test member is "adhesion amount (mg / test piece)", and the fixing amount is "Fixed amount (mg/test piece)" and the percentage (%) of the value obtained by dividing this fixed amount by the adhered amount is shown in Table 13 below as "Fixed amount/adhered amount (%)".
In Table 13, benzalkonium chloride is indicated as "BZC", 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane bromide is indicated as "hygenia", and cetylpyridinium chloride is indicated as "CPC". .
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　表１３に示すとおり、（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を併用する本発明の抗菌抗カビ組成物の具体例である実施例試験検体ｃ～ｊは、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分の付着量が、（Ａ）油溶性抗菌成分のみを含有する比較例試験検体ｂ～ｇに比べて、約１．１～１．３倍に向上することが明らかとなった。本試験においても、（Ａ）油溶性抗菌成分として抗菌性香料成分を用いても、（Ｂ）カチオン型抗菌成分を併用することにより、湿潤環境に存在する対象物に対する（Ａ）油溶性抗菌成分の付着量が大きく向上する効果が得られることが確認された。
　また、本発明の抗菌抗カビ組成物の具体例である実施例試験検体ｃ～ｋは、日本における浴室の壁材を模したモルタル板の試験部材への（Ａ）油溶性抗菌成分の定着量が、付着量に対して５８～８７％であった。この結果から、実施例ｃ～ｋの（Ａ）油溶性抗菌成分の定着量／付着量（％）の値は、対応する比較例ｂ～ｇの（Ａ）油溶性抗菌成分の定着量／付着量（％）と比べて１．１～１．５倍と定着性に優れるものであることが明らかとなった。すなわち、本発明における（Ａ）油溶性抗菌成分として抗菌性香料成分を採用した場合においても、湿潤環境に存在する対象物に対する優れた定着性を実現できることが確認された。また、（Ａ）油溶性抗菌成分として抗菌性香料成分のみを含有する比較例試験検体ｂ～ｇに比べて、湿潤環境に存在する対象物への定着性に優れることも確認された。 As shown in Table 13, example test specimens c to j, which are specific examples of the antibacterial and antifungal composition of the present invention that uses (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, were used in bathrooms in Japan. The adhesion amount of (A) the oil-soluble antibacterial component to the test member of the mortar plate imitating the wall material is about 1.1 compared to the comparative test specimens b to g containing only the (A) oil-soluble antibacterial component. It was clarified that it improved by ~1.3 times. In this test, even if an antibacterial fragrance component is used as (A) an oil-soluble antibacterial component, (B) a cationic antibacterial component is used in combination with (A) an oil-soluble antibacterial component against an object existing in a moist environment. It was confirmed that the effect of greatly improving the adhesion amount of was obtained.
In addition, example test specimens c to k, which are specific examples of the antibacterial and antifungal composition of the present invention, are the amount of (A) the oil-soluble antibacterial component fixed to the test member of a mortar plate imitating the wall material of a Japanese bathroom. was 58 to 87% of the adhesion amount. From this result, the values of (A) the amount of fixation/adhesion (%) of the oil-soluble antibacterial component in Examples c to k correspond to the amounts of fixation/adhesion (%) of the (A) oil-soluble antibacterial component in Comparative Examples b to g. It was found to be 1.1 to 1.5 times as high as the amount (%) and to be excellent in fixability. That is, it was confirmed that even when an antibacterial fragrance component was employed as (A) the oil-soluble antibacterial component in the present invention, excellent fixability to objects existing in a wet environment could be achieved. In addition, it was also confirmed that compared to the comparative test specimens b to g containing only the antibacterial fragrance component as the (A) oil-soluble antibacterial component, the fixability to objects in a wet environment is excellent.
＜抗菌抗カビ組成物の部材への影響確認試験＞
（１）試験検体
　上記「付着量向上効果確認試験－１」で使用した実施例１及び比較例１の試験検体を使用した。
　また、試験部材として、アクリル樹脂板（株式会社光製、スミホリデーＡ０００－２ＳＳ）とＡＢＳ樹脂板（日本テストパネル株式会社製）、それぞれ５ｃｍ×５ｃｍとして使用した。
（２）試験方法
　実施例１、比較例１の試験検体それぞれを、各試験部材に各１０μＬ滴下して、５分間放置した。その後、各試験部材表面の試験検体を拭き取り、試験検体表面の状態を目視で観察した。
（３）結果
　実施例１の試験検体は、アクリル樹脂板とＡＢＳ樹脂板ともに影響が確認されなかった。一方、比較例１の試験検体は、アクリル樹脂板とＡＢＳ樹脂板ともに白化や試験部材表面の凹凸化などの影響が確認された。これは、（Ａ）油溶性抗菌成分である４－イソプロピル－３－メチルフェノールが、試験部材の内部に浸透しやすく、そのため、試験部材の内部が膨潤して白化や試験部材表面が凹凸化したものと推察される。
　実施例１の試験検体が、比較例１同様に（Ａ）油溶性抗菌成分である４－イソプロピル－３－メチルフェノールを含有するにもかかわらず、試験部材に対して大きな影響を及ぼさなかった理由としては、（Ｂ）カチオン型抗菌成分である塩化ベンザルコニウムとの併用により、４－イソプロピル－３－メチルフェノールが試験部材の内部への浸透が抑制され、試験部材表面に留まったことに起因するものと考えられる。
　本発明における（Ａ）油溶性抗菌成分は、浴室の小物や排水口等に用いられるアクリル樹脂やＡＢＳ樹脂等のプラスチック材に対して白化や膨潤などの外観上の影響を引き起こす可能性があるものの、（Ａ）油溶性抗菌成分と（Ｂ）カチオン型抗菌成分を併用することにより、（Ｂ）カチオン型抗菌成分は、プラスチック材に（Ａ）油溶性抗菌成分が浸透することを抑制し、プラスチック材の白化や膨潤といった外観上の劣化を軽減することが、上記試験結果により確認された。 <Confirmation test of the effect of the antibacterial and antifungal composition on members>
(1) Test Specimen The test specimens of Example 1 and Comparative Example 1 used in the above-mentioned "adhesion amount improvement effect confirmation test-1" were used.
As test members, an acrylic resin plate (manufactured by Hikari Co., Ltd., Sumiholiday A000-2SS) and an ABS resin plate (manufactured by Nippon Test Panel Co., Ltd.), each measuring 5 cm×5 cm, were used.
(2) Test method 10 µL of each of the test specimens of Example 1 and Comparative Example 1 was dropped onto each test member and left for 5 minutes. After that, the test sample on the surface of each test member was wiped off, and the state of the test sample surface was visually observed.
(3) Results In the test specimen of Example 1, no influence was confirmed on both the acrylic resin plate and the ABS resin plate. On the other hand, in the test specimen of Comparative Example 1, both the acrylic resin plate and the ABS resin plate were affected by whitening and roughening of the surface of the test member. This is because (A) 4-isopropyl-3-methylphenol, which is an oil-soluble antibacterial component, easily penetrates into the inside of the test member, so that the inside of the test member swells and whitens and the surface of the test member becomes uneven. It is assumed that
The reason why the test sample of Example 1 did not have a large effect on the test member even though it contained (A) 4-isopropyl-3-methylphenol, which is an oil-soluble antibacterial component, as in Comparative Example 1. As (B) combined use with benzalkonium chloride, which is a cationic antibacterial component, 4-isopropyl-3-methylphenol was suppressed from penetrating into the interior of the test member and remained on the surface of the test member. It is considered that
The (A) oil-soluble antibacterial component in the present invention may cause external effects such as whitening and swelling on plastic materials such as acrylic resins and ABS resins used for bathroom accessories and drains. , By using (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component in combination, (B) the cationic antibacterial component suppresses the penetration of (A) the oil-soluble antibacterial component into the plastic material, and the plastic It was confirmed by the above test results that deterioration in appearance such as whitening and swelling of the material is reduced.
　本発明の抗菌抗カビ組成物は、油溶性（非水溶性）の抗菌剤である（Ａ）油溶性抗菌成分と水溶性の抗菌剤である（Ｂ）カチオン型抗菌成分を併用することにより、（Ａ）油溶性抗菌成分のみならず（Ｂ）カチオン型抗菌成分をも、湿潤環境に存在する対象物への付着量を向上させることができ、さらに、湿潤環境に存在する対象物への定着量をも向上させることができるので、長期間にわたり優れた抗微生物効果を得ることができ極めて有用である。
　また、本発明の噴霧剤は、簡便に湿潤環境に存在する対象物に抗菌抗カビ組成物を付着、定着させることが可能なため、非常に有用である。
　１．（Ｂ）カチオン型抗菌成分を有効成分とする、噴霧粒子付着面における（Ａ）油溶性抗菌成分の定着向上剤。
　２．（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を含有する組成物を用いた、噴霧粒子付着面におけるフェノール化合物の定着を向上させる方法。
　３．（Ｂ）カチオン型抗菌成分を有効成分とする、噴霧粒子付着面におけるフェノール化合物の定着向上剤。
　４．フェノール化合物及び（Ｂ）カチオン型抗菌成分を含有する組成物を用いた、噴霧粒子付着面におけるフェノール化合物の定着を向上させる方法。
　５．液体担体を有効成分とする、（Ｂ）カチオン型抗菌成分の刺激緩和剤。 The antibacterial and antifungal composition of the present invention is an oil-soluble (water-insoluble) antibacterial agent (A) an oil-soluble antibacterial component and a water-soluble antibacterial agent (B) a cationic antibacterial component. Not only (A) the oil-soluble antibacterial component but also (B) the cationic antibacterial component can improve the amount of adhesion to the object present in the wet environment, and furthermore, it can be fixed to the object present in the wet environment. Since the amount can also be increased, excellent antimicrobial effects can be obtained over a long period of time, which is extremely useful.
In addition, the spray of the present invention is very useful because it allows the antibacterial and antifungal composition to be easily adhered to and fixed to an object existing in a wet environment.
1. (B) A fixation improver for (A) an oil-soluble antibacterial component on the spray particle adhering surface, containing a cationic antibacterial component as an active ingredient.
2. A method for improving fixation of a phenolic compound on a spray particle adhesion surface using a composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component.
3. (B) A fixation improver for a phenolic compound on the sprayed particle adhesion surface containing a cationic antibacterial component as an active ingredient.
4. A method for improving fixation of a phenolic compound on a spray particle adhesion surface using a composition containing a phenolic compound and (B) a cationic antibacterial component.
5. (B) a cationic antibacterial ingredient stimulus mitigating agent containing a liquid carrier as an active ingredient.

Claims (2)

  1. 　（Ａ）油溶性抗菌成分及び（Ｂ）カチオン型抗菌成分を含有する、抗菌抗カビ組成物。 An antibacterial and antifungal composition containing (A) an oil-soluble antibacterial component and (B) a cationic antibacterial component.
  2. 　請求項１に記載の抗菌抗カビ組成物を噴霧容器に充填した、噴霧剤。



          A spray containing the antibacterial and antifungal composition according to claim 1 in a spray container.
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JPH0616511A (en) * 1991-01-31 1994-01-25 Kiyasupa Kk Antigermical agent and its production
JPH11286405A (en) * 1998-03-31 1999-10-19 Dainippon Jochugiku Co Ltd Fungicide
JP2000355512A (en) * 1999-06-14 2000-12-26 S T Chem Co Ltd Environment antimicrobial agent and production of antimicrobial substance
JP2006151908A (en) * 2004-11-30 2006-06-15 Lion Corp Composition for suppressing slime and method for suppressing slime
JP2007306978A (en) * 2006-05-16 2007-11-29 Aasu Biochem Kk Deodorant
JP2017002007A (en) * 2015-06-15 2017-01-05 大日本除蟲菊株式会社 Aqueous antifungal agent
JP2017039646A (en) * 2015-08-17 2017-02-23 大日本除蟲菊株式会社 Bactericidal efficacy enhancer and liquid bactericidal composition comprising the same
JP2019151735A (en) * 2018-03-02 2019-09-12 花王株式会社 Fungicide detergent composition for hard surface
JP2021166821A (en) * 2020-03-13 2021-10-21 大日本除蟲菊株式会社 Quantitative injection aerosol product for controlling specific harmful materials and method for controlling specific harmful materials using the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0616511A (en) * 1991-01-31 1994-01-25 Kiyasupa Kk Antigermical agent and its production
JPH11286405A (en) * 1998-03-31 1999-10-19 Dainippon Jochugiku Co Ltd Fungicide
JP2000355512A (en) * 1999-06-14 2000-12-26 S T Chem Co Ltd Environment antimicrobial agent and production of antimicrobial substance
JP2006151908A (en) * 2004-11-30 2006-06-15 Lion Corp Composition for suppressing slime and method for suppressing slime
JP2007306978A (en) * 2006-05-16 2007-11-29 Aasu Biochem Kk Deodorant
JP2017002007A (en) * 2015-06-15 2017-01-05 大日本除蟲菊株式会社 Aqueous antifungal agent
JP2017039646A (en) * 2015-08-17 2017-02-23 大日本除蟲菊株式会社 Bactericidal efficacy enhancer and liquid bactericidal composition comprising the same
JP2019151735A (en) * 2018-03-02 2019-09-12 花王株式会社 Fungicide detergent composition for hard surface
JP2021166821A (en) * 2020-03-13 2021-10-21 大日本除蟲菊株式会社 Quantitative injection aerosol product for controlling specific harmful materials and method for controlling specific harmful materials using the same

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