WO2020090351A1 - Composition, modified base material, wet wipes, and spray - Google Patents

Composition, modified base material, wet wipes, and spray Download PDF

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Publication number
WO2020090351A1
WO2020090351A1 PCT/JP2019/039420 JP2019039420W WO2020090351A1 WO 2020090351 A1 WO2020090351 A1 WO 2020090351A1 JP 2019039420 W JP2019039420 W JP 2019039420W WO 2020090351 A1 WO2020090351 A1 WO 2020090351A1
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Prior art keywords
composition
mass
antibacterial agent
composition according
antibacterial
Prior art date
Application number
PCT/JP2019/039420
Other languages
French (fr)
Japanese (ja)
Inventor
冨澤　秀樹
Original Assignee
富士フイルム株式会社
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Publication of WO2020090351A1 publication Critical patent/WO2020090351A1/en

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Classifications

    • 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
    • A01N25/24—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 ingredients to enhance the sticking of the active ingredients
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • D06M13/507—Organic silicon compounds without carbon-silicon bond
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/16—Cloths; Pads; Sponges

Definitions

  • the present invention relates to compositions, modified substrates, wet wipes and sprays.
  • Patent Document 1 discloses a coating obtained by curing a composition containing a hydrophilic polymer, a photoinitiator, particles containing metallic silver (Ag), and a carrier liquid.
  • the present inventor produced a coating containing an antibacterial agent described in Patent Document 1 on a substrate and examined its characteristics. As a result, the antibacterial agent was easily peeled off from the substrate, and it was found that the antibacterial agent has improved adhesion. I found that there is room.
  • an object of the present invention to provide a composition capable of imparting excellent antibacterial properties to a base material and having excellent adhesion of the antibacterial agent applied to the base material.
  • Another object of the present invention is to provide a modified base material, a wet wiper, and a spray.
  • a composition containing an antibacterial agent and a siloxane compound (2)
  • the antibacterial agent is in the form of particles, The composition according to (1), wherein the antibacterial agent has an average particle size of 1.0 ⁇ m or less.
  • the composition according to (1) or (2), wherein the antibacterial agent is a composite particle containing inorganic particles and an organic antibacterial agent carried on the inorganic particles.
  • (4) Furthermore, including a solvent, The composition according to any one of (1) to (3), wherein the solvent consists essentially of water.
  • the composition according to any one of (1) to (4), wherein the siloxane compound is a compound represented by the formula (X) described below.
  • (6) The composition according to any one of (1) to (5), which further contains a silane coupling agent.
  • a wet wiper comprising a base cloth and the composition according to any one of (1) to (6) impregnated into the base cloth.
  • a spray comprising a spray container and the composition according to any one of (1) to (6) contained in the spray container.
  • the composition which can provide the base material with the outstanding antibacterial property and is excellent in the adhesiveness of the antibacterial agent applied to the base material can be provided.
  • a modified base material, a wet wiper, and a spray can be provided.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This has the same meaning for each compound.
  • (meth) acrylate represents acrylate and / or methacrylate (either one or both of acrylate and methacrylate)
  • (meth) acryloyl means acryloyl and / or methacryloyl (of acryloyl and methacryloyl). Either one or both).
  • a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.
  • the antibacterial agent is not particularly limited, and examples thereof include known organic antibacterial agents and / or inorganic antibacterial agents.
  • the organic antibacterial agent is not particularly limited, and examples thereof include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium compounds, pyridine compounds, triazine compounds, Examples thereof include benzoisothiazoline compounds and isothiazoline compounds.
  • the organic antibacterial agent also includes a natural antibacterial agent. Examples of natural antibacterial agents include chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the shells of crabs and / or shrimps.
  • the inorganic antibacterial agent is not particularly limited, and examples thereof include a metal simple substance, a metal ion, an inorganic substance containing a metal, and a composite particle containing an inorganic carrier and a metal or organic antibacterial agent supported on the inorganic carrier. Be done.
  • the metal contained in the composite particles may be a simple metal or a metal ion.
  • the type of metal contained in the inorganic antibacterial agent is not particularly limited, and examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like.
  • silver, copper, zinc, aluminum or zirconium is preferable, silver, copper, zinc or aluminum is more preferable, silver or copper is further preferable, and silver is particularly preferable.
  • the inorganic substance containing a metal include a metal oxide, a metal nitride, a metal halide, a metal cyanide, a metal selenide, a metal sulfide, a metal telluride, and a metal salt. Is mentioned.
  • the metal salt include arsenate, hydrogen fluoride, bromate, chlorate, chromate, cyanate, hexafluoroantimonate, hexafluoroarsenate and hexafluorophosphate.
  • examples thereof include salts, tetrafluoroborates, tetratungstates, thiocyanates and vanadates.
  • the type of inorganic carrier in the composite particles is not particularly limited, for example, zinc calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated alumina, silicon oxide, silicate glass, borosilicate.
  • examples thereof include glass, phosphate glass, zeolite (crystalline aluminosilicate salt), apatite, hydroxyapatite, titanium phosphate, potassium titanate, hydrous bismuth oxide, hydrous zirconium oxide, hydrotalcite, and activated carbon.
  • silicon oxide silicon oxide
  • synthetic amorphous silica is preferable.
  • Synthetic amorphous silica is roughly classified into those produced by a dry method and those produced by a wet method.
  • the former includes dry silica, and the latter includes wet silica, silica gel, and colloidal silica.
  • dry silica is preferred.
  • the dry silica for example, those sold under the trade name Aerosil by Nippon Aerosil Co., Ltd. are preferably used.
  • the inorganic carrier may be crystalline or amorphous (amorphous), but is preferably amorphous and more preferably glass.
  • materials that can form the glass include silicates, borosilicates, and phosphates.
  • Aluminum silicate is preferable as the silicate.
  • the aluminum silicate may be a natural product or a synthetic product.
  • a compound represented by the following formula (A) is preferable.
  • n is a positive number of 6 or more (preferably 6 to 50)
  • m is a positive number of 1 to 20.
  • Examples of the kind of metal contained in the composite particles include the kind of metal contained in the above-mentioned inorganic antibacterial agent.
  • Examples of the organic antibacterial agent contained in the composite particles include known organic antibacterial agents, and examples thereof include the above-mentioned organic antibacterial agents. Of these, hydroxamic acid derivatives, quaternary ammonium compounds, triclosan, and zinc (Zn) pyrithione are preferable.
  • hydroxamic acid derivative examples include cyclic hydroxamic acid derivatives, and more specifically, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) -pyridone monoethanolamine Salts (also known as piroctone ethanolamine), 6-cyclohexyl-1-hydroxy-4-methyl-2 (1H) -pyridone, 2-hydroxyethanamine, pyridonecarboxylic acid compounds (eg, pyromidic acid, pipemidic acid, sinoxacin) ) Is mentioned.
  • 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) -pyridone monoethanolamine Salts also known as piroctone ethanolamine
  • 6-cyclohexyl-1-hydroxy-4-methyl-2 (1H) -pyridone 2-hydroxyethanamine
  • pyridonecarboxylic acid compounds eg, pyromidic acid, pipemidic acid, sinoxacin
  • quaternary ammonium compound examples include quaternary ammonium compounds having a long-chain alkyl group having 1 to 18 carbon atoms, and more specifically, benzalkonium cetyl phosphate, benzalkonium chloride, benzethonium chloride, chloride Examples include methylbenzethonium, cetylpyridinium chloride, cetrimonium, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, and domiphen bromide.
  • metal-supported zeolite metal-supported apatite, metal-supported glass, metal-supported zirconium phosphate, or metal-supported calcium silicate is preferable, and metal-supported glass is more preferable.
  • the average particle diameter of the antibacterial agent is not particularly limited, but it is often 3.0 ⁇ m or less, preferably 1.0 ⁇ m or less, and more preferably 0.6 ⁇ m or less.
  • the lower limit is not particularly limited, it is often 0.01 ⁇ m or more, and more often 0.2 ⁇ m or more.
  • the average particle size can be measured by observing with an electron microscope.
  • the average particle diameter is defined as a primary particle and a secondary particle (the “secondary particle” is defined as an aggregate formed by fusing or contacting the primary particles with each other, with respect to the antibacterial agent particle. .)
  • the 50% volume cumulative diameter (D50) is measured three times using a laser diffraction / scattering type particle size distribution measuring device manufactured by Horiba Ltd., and the value is measured three times. You may substitute the average value of the above as an average particle diameter.
  • the average particle size of the particulate antibacterial agent can be adjusted by a conventionally known method, and for example, dry pulverization or wet pulverization can be adopted.
  • dry pulverization for example, a mortar, jet mill, hammer mill, pin mill, rotary mill, vibration mill, planetary mill, bead mill, etc. are appropriately used.
  • wet pulverization various ball mills, high-speed rotary pulverizers, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, etc. are used as appropriate.
  • the above antibacterial agent can be produced by a known method, and a commercially available product may be used.
  • the antibacterial agents may be used alone or in combination of two or more kinds.
  • the content of the antibacterial agent in the composition is not particularly limited, but is preferably 0.001 to 55% by mass with respect to the total solid content of the composition, and 0.001 to 50 mass% is more preferable, and 0.01 to 40 mass% is still more preferable.
  • a siloxane compound is a compound having a Si-O-Si bond.
  • the siloxane compound include a hydrolyzate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a compound selected from the group consisting of hydrolyzed condensates, and more specifically, the following formulas At least one selected from the group consisting of a hydrolyzate of the compound represented by (1) and a hydrolyzed condensate thereof.
  • Formula (1) Si- (OR) 4 In the above formula (1), R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different.
  • Examples of the compound represented by the above formula (1) include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate and tetra-t.
  • -Butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate, etc. are mentioned.
  • the hydrolyzate of the compound represented by the formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by the formula (1).
  • the above-mentioned hydrolyzate is one in which all of the OR groups are hydrolyzed (complete hydrolyzate), but some of the OR groups is hydrolyzed (partial hydrolyzate). May be. That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
  • the hydrolytic condensate of the compound represented by the formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by the formula (1) and condensing the obtained hydrolyzate. Intended.
  • hydrolysis-condensation product even if all the OR groups are hydrolyzed and all the hydrolysis products are condensed (complete hydrolysis-condensation product), some of the OR groups are hydrolyzed. It may be decomposed and a part of the hydrolyzed product may be condensed (partial hydrolyzed condensate). That is, the hydrolysis-condensation product may be a complete hydrolysis-condensation product, a partial hydrolysis-condensation product, or a mixture thereof.
  • siloxane compound a compound represented by the formula (X) is preferable.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms.
  • n represents an integer of 2 or more.
  • n is preferably an integer of 5 or more, more preferably an integer of 8 or more.
  • the upper limit is not particularly limited, but an integer of 100 or less is preferable, and an integer of 20 or less is more preferable.
  • Examples of commercially available compounds represented by the above formula (X) include “Ethyl silicate 48”, “Methyl silicate 51”, “Methyl silicate 53A” manufactured by Colcoat, and “MKC silicate MS51” manufactured by Mitsubishi Chemical. Examples thereof include “MKC silicate MS56” and “MKC silicate MS57”.
  • the siloxane compounds may be used alone or in combination of two or more.
  • the content of the siloxane compound in the composition is not particularly limited, but is preferably 20 to 99.8 mass%, more preferably 20 to 90 mass%, and more preferably 40 to 99 mass% with respect to the total solid content of the composition. Is more preferable.
  • composition may contain other components within the range in which the effects of the present invention are exhibited.
  • the composition of the present invention may include a solvent.
  • the solvent is not particularly limited, and examples thereof include water and / or an organic solvent.
  • the organic solvent methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and , Alcohol solvents such as myristyl alcohol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Ethylene glycol monobutyl ether, diethylene glycol G
  • the content of the alcoholic solvent is 5% by mass or more based on the total mass of the composition, in that the sedimentation of the particulate matter is suppressed and the deodorant property of the formed film is more excellent.
  • Is preferable and 10 mass% or more is preferable.
  • the upper limit is not particularly limited, but for example, preferably 99% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 45% by mass or less.
  • the content of the alcohol in the solvent is not particularly limited, but is preferably 0.001 to 100% by mass, and 0.01 to 90% by mass with respect to the total mass of the solvent. Is more preferable, 5 to 90% by mass is further preferable, and 5 to 80% by mass is particularly preferable.
  • the solvent consists essentially of water.
  • substantially means that the content of water is 99% by mass or more, preferably 99.5% by mass or more, and preferably 100% by mass, with respect to the total mass of the solvent. More preferable.
  • the content of the solvent in the composition is not particularly limited, but the solid content of the composition is preferably adjusted to 0.001 to 80 mass% from the viewpoint that the composition has more excellent coatability. It is more preferably adjusted to 0.01 to 10% by mass, and further preferably adjusted to 0.1 to 5.0% by mass.
  • the solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, the total content is preferably within the above range.
  • the composition of the present invention may contain a silane coupling agent.
  • the type of functional group contained in the silane coupling agent is not particularly limited, and examples thereof include a glycidyl group, an amino group, a vinyl group, a (meth) acryloyl group, a mercapto group, and an isocyanate group.
  • a compound represented by the formula (Y) is preferable.
  • Formula (Y) R 5 -L-Si (OR 6 ) 3 R 5 represents a glycidyl group, an amino group, a vinyl group, a (meth) acryloyl group, a mercapto group, or an isocyanate group.
  • L represents a divalent linking group.
  • the divalent linking group include an alkylene group, —NH—, —O—, —CO—, —CO 2 —, —S—, —SO 3 —, or a divalent group combining these.
  • R 6 represents an alkyl group.
  • the carbon number of the alkyl group is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
  • the composition may include a dispersant.
  • the dispersant is not particularly limited, and known dispersants can be used.
  • a nonionic or anionic dispersant is preferable, and a dispersant having an anionic polar group such as a carboxy group, a phosphoric acid group, and a hydroxyl group (an anionic dispersant) is more preferable.
  • a commercial item can be used as an anionic dispersant.
  • the content of the dispersant in the composition is not particularly limited, but is, for example, 70% by mass or less, and preferably 50% by mass or less, based on the total solid content of the composition.
  • the lower limit is not particularly limited, but is, for example, 0.01% by mass or more, preferably 1.0% by mass or more, and more preferably 15% by mass or more from the viewpoint that the deodorant property of the formed film is more excellent.
  • the dispersants may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.
  • the composition may include a catalyst that accelerates the condensation of the siloxane compound (hereinafter also referred to as “reaction catalyst”).
  • the catalyst is not particularly limited, but examples thereof include an alkali catalyst and an organometallic catalyst.
  • the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
  • the organic metal catalyst include aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate).
  • the catalyst is preferably an organometallic catalyst, and among them, an aluminum chelate compound or a zirconium chelate compound is more preferable, and an aluminum chelate compound is further preferable. preferable.
  • the content of the catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and still more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition. ..
  • the catalyst may be used alone or in combination of two or more. When two or more catalysts are used in combination, the total content is preferably within the above range.
  • the composition may include a surfactant.
  • the surfactant has a function of improving the coating property of the composition.
  • the surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • the content of the surfactant is not particularly limited, but is preferably 0.01 part by mass or more based on 100 parts by mass of the total solid content of the composition.
  • the upper limit of the content of the surfactant is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 4 parts by mass or less with respect to 100 parts by mass of the total solid content of the composition. More preferable.
  • the surfactants may be used alone or in combination of two or more. When two or more kinds are used in combination, the total content thereof is preferably within the above range.
  • nonionic surfactant examples include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, and polyethylene glycol monostearyl ester.
  • the ionic surfactants include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates and alkyl phosphates; cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts; Examples include amphoteric surfactants such as alkylcarboxybetaine.
  • the composition may include a fragrance.
  • flavors flavors H-1, H-2, H-3, H-4, H-6, H-9, H-10, H-11, H-12, H-13, H manufactured by Hasegawa Fragrance Co., Ltd. -14, flavors made by Takasago International Corporation T-100, T-101, T-102, T-103, T-104, T-105, T-106, T-107, EDA-171, Soda Aroma Co., Ltd.
  • Flavor S-201, flavor DA-40 manufactured by Riken Fragrance Industry Co., Ltd. and the like can be mentioned.
  • the content of the fragrance is preferably 0.01 to 5 mass% with respect to the total mass of the composition.
  • other components include film-forming agents, deodorants, ultraviolet absorbers, preservatives, pH adjusters, defoamers, polymerization initiators, catalysts, photocatalytic materials, fillers, antiaging agents.
  • film-forming agents deodorants, ultraviolet absorbers, preservatives, pH adjusters, defoamers, polymerization initiators, catalysts, photocatalytic materials, fillers, antiaging agents.
  • additives such as antistatic agents, flame retardants, adhesion promoters, leveling agents, matting agents, light stabilizers, dyes, and pigments can be used.
  • the pH of the above composition is not particularly limited, but it is preferable to adjust the pH to an appropriate range in consideration of rough hands of the user in an actual use environment.
  • the pH of the above composition is generally preferably 2.0 to 12.0, more preferably 3.0 to 11.0, and even more preferably 6.0 to 8.0.
  • a method of adjusting the pH of the composition a method of adding an acid or an alkali to the above composition can be mentioned.
  • the pH can be measured in a 25 ° C. environment using a commercially available pH measuring meter (eg, pH meter HM-30R manufactured by Toa DKK Co., Ltd.).
  • the viscosity of the composition is not particularly limited and may be adjusted according to the application.
  • the viscosity of the composition at 25 ° C. is preferably 250 cP or higher, more preferably 300 cP or higher, even more preferably 400 cP or higher.
  • the upper limit is, for example, 500 cP or less.
  • the viscosity can be measured using Toki Sangyo Co., Ltd. VISCOMETER TUB-10 or Sekonic SEKONIC VISCOMETER.
  • the composition can be prepared by appropriately mixing the above-mentioned essential components and optional components.
  • the order of mixing the above components is not particularly limited.
  • an antibacterial part By applying the composition to a substrate, an antibacterial part can be formed on the substrate. That is, a modified base material having a base material and an antibacterial part arranged on the base material is obtained.
  • the antibacterial part means a part formed by using the composition described above, and contains at least an antibacterial agent and a binder derived from a siloxane compound.
  • the method of applying the composition to the substrate is not particularly limited, and known coating methods can be mentioned, for example, spray, roll coater, gravure coater, screen, spin coater, flow coater, inkjet, electrostatic coating, and wipe. Etc. Of these, spraying or wiping is preferable. Examples of the wiping method include a method of impregnating a base cloth such as a non-woven fabric with the above composition and then wiping the surface of the base material with the above base cloth.
  • the composition applied on the substrate may be subjected to a drying treatment, if necessary.
  • a drying treatment include heat treatment.
  • the type of the base material is not particularly limited as long as it plays a role of supporting the antibacterial part.
  • the shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, a fiber structure shape, and a particle shape.
  • that the shape of the base material is a fibrous structure means that the base material is composed of fibers such as a non-woven fabric or a woven fabric.
  • the material forming the base material is not particularly limited, and examples thereof include metal, glass, ceramics, and plastic (resin). Among them, plastic is preferable from the viewpoint of handleability. Examples of the plastic include polyolefin (polyethylene, polypropylene), cellulose, polystyrene, polyamide, polyimide, and poly (meth) acrylate.
  • the position of the antibacterial part formed on the base material is not particularly limited, and even if it is a film-like structure arranged so as to cover the entire surface of the base material, it is arranged in a dotted pattern on the base material. Good.
  • the film thickness of the antibacterial part is not particularly limited, but is preferably 0.001 to 50 ⁇ m, more preferably 0.01 to 10 ⁇ m.
  • the said film thickness intends the value which measured the thickness in the position of arbitrary 10 points
  • a wet wiper according to an embodiment of the present invention includes a base cloth and a composition in which the base cloth is impregnated.
  • the composition is as described above.
  • the base cloth is not particularly limited, and may be formed of natural fibers or chemical fibers.
  • the natural fiber include pulp, cotton, hemp, flax, wool, quills, cashmere, mohair, and silk.
  • the chemical fiber material include rayon, polynosic, acetate, triacetate, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyalkylene paraoxybenzoate, and polyclar. Be done.
  • the hydrophilic base cloth is preferable among these base cloths because it is easily impregnated with the composition.
  • the hydrophilic base cloth is, for example, a base cloth including fibers having a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amide group, and a sulfonyl group.
  • a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amide group, and a sulfonyl group.
  • Specific examples of the hydrophilic base cloth include vegetable fiber, cotton, pulp, animal fiber, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.
  • non-woven cloth, cloth, towel, gauze, absorbent cotton, etc. may be used, and non-woven cloth is preferable.
  • the basis weight (mass per unit area) of the base fabric is preferably 100 g / m 2 or less.
  • the amount of impregnation when the above composition is impregnated into the base cloth is preferably at least 1 time the mass of the base cloth.
  • the spray which concerns on embodiment of this invention has a spray container and the composition accommodated in the said spray container.
  • the composition is as described above.
  • An example of the spray of the present invention is a form in which the above composition and a propellant are filled in a predetermined container.
  • the propellant used is not particularly limited, but examples thereof include liquefied petroleum gas.
  • composition of the present invention can be used for products such as softeners, detergents, shampoos, rinses, etc., which are related to deodorant and / or antibacterial.
  • Antibacterial activity value is 3.5 or more
  • A Antibacterial activity value is 3.0 or more and less than 3.5
  • B Antibacterial activity value is 2.0 or more and less than 3.0
  • C Antibacterial activity value is 1.0 or more and less than 2.0
  • D Antibacterial activity value is less than 1.0
  • the composition 1 (0.6 g) was sprayed onto 3 x 5 cm of the antibacterial evaluation non-woven fabric (made of cellulose), and the treatment of drying for 1 hour was repeated 3 times (spraying 1.8 g in total), then for 12 hours at room temperature And dried to prepare a sample.
  • the obtained sample was immersed in 10 g of water and shaken for 1 hour. Then, the sample was taken out, and the residual adherence rate of the antibacterial agent contained in the sample taken out from water was measured based on the amount of the antibacterial agent contained in the sample before being immersed in water.
  • A Residual adhesion rate is 85% or more
  • B Residual adhesion rate is 70% or more and less than 85%
  • C Residual adhesion rate is 50% or more and less than 70%
  • D Residual adhesion rate is 30% or more and less than 50%
  • E residual adhesion rate is less than 30%
  • Tables 1 to 4 described below the types and contents of the components in the composition to be used, and the resin of the base material of the non-woven fabric used in (Evaluation of antibacterial property) and (Evaluation of adhesiveness) Compositions 2 to 33 were manufactured according to the same procedure as in Example 1 except that the kind and the like were changed, and various evaluations were performed.
  • the symbols shown in Tables 1 to 4 represent the following.
  • Silver antibacterial agent (Novalon): silver-supported zirconium phosphate ("Tobaro Gosei Co., Ltd.” Novalon AG300 ”) controlled to a predetermined particle size shown in the table.
  • Copper antibacterial agent (NS-20C): Copper-supported aluminum silicate glass (manufactured by Toagosei Co., Ltd., "Kesmon (registered trademark) NS-20C")
  • Silica + benzelkonium chloride Octopirox (registered trademark, piroctone ethanolamine) manufactured by Clariant Co., Ltd. adheres to the surface of the silica fine particles produced by the procedure of Example 1 of JP-A-2017-101084.
  • Silica + Zn pyrithione composite particles produced by referring to the procedure in Example 1 of JP-A-2017-101084 and having Zn pyrithione attached to the surface of silica fine particles.
  • MS-57 Siloxane compound (corresponds to the compound represented by the formula (X), “MKC (registered trademark) silicate” MS-57 manufactured by Mitsubishi Chemical Corporation.
  • KBM403 3-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., silane coupling agent)
  • KBM903 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., silane coupling agent)
  • each of Compositions 1 to 33 was subjected to a reduced pressure treatment to distill off ethanol in the composition. Then, the weight reduced by distillation was replaced with water to prepare compositions 34 to 66 in which the water content in the solvent was 99% by mass or more. The content of water in the obtained composition was 99% by mass or more, and it was confirmed by gas chromatography that the content of ethanol was 1% by mass or less.
  • compositions 34 to 66 were subjected to antibacterial property evaluation and sticking property evaluation as Examples 34 to 66, and Examples 1 to 33 using Compositions 1 to 33 containing ethanol were respectively performed. The same evaluation result as was obtained.
  • the antibacterial property evaluation was performed in the same manner except that the step of mixing with an aqueous solution of 60% by mass of ethanol was changed to mixing with pure water.
  • composition was prepared by replacing all the ethanol in the composition 4 used in Example 4 with water, and the following hydrophilicity evaluation was performed together with the composition used in Example 4.
  • the evaluation using the composition used in Example 4 is “C”
  • the evaluation using the composition in which all the ethanol in the composition used in Example 4 is replaced with water is “A”. Met.

Abstract

Provided is a composition which can impart excellent antimicrobial properties to a base material and ensures excellent attachment of the antimicrobial agent to the base material. Also provided are a modified base material, a wet wiper, and a spray. The composition contains an antimicrobial agent and a siloxane compound.

Description

組成物、修飾基材、ウェットワイパー、スプレーCompositions, modified substrates, wet wipes, sprays

　本発明は、組成物、修飾基材、ウェットワイパー、及び、スプレーに関する。
The present invention relates to compositions, modified substrates, wet wipes and sprays.

　銀等に代表される抗菌剤は、様々な用途に用いられている。

　特許文献１には、親水性ポリマー、光開始剤、金属銀（Ａｇ）を含む粒子、及び、キャリヤ液を含む配合物を硬化させて得られるコーティングを開示している。
Antibacterial agents represented by silver and the like are used for various purposes.

Patent Document 1 discloses a coating obtained by curing a composition containing a hydrophilic polymer, a photoinitiator, particles containing metallic silver (Ag), and a carrier liquid.

特表２０１０－５０３７３７号公報Japanese Patent Publication No. 2010-503737

　本発明者は、特許文献１に記載された抗菌剤を含むコーティングを基材上に作製して、その特性について検討したところ、抗菌剤が基材から剥がれやすく、抗菌剤の固着性に関して改善の余地があることを知見した。
The present inventor produced a coating containing an antibacterial agent described in Patent Document 1 on a substrate and examined its characteristics. As a result, the antibacterial agent was easily peeled off from the substrate, and it was found that the antibacterial agent has improved adhesion. I found that there is room.

　本発明は、上記実情に鑑みて、基材に対して優れた抗菌性を付与でき、基材に付与された抗菌剤の固着性に優れる組成物を提供することを課題とする。

　また、本発明は、修飾基材、ウェットワイパー、及び、スプレーを提供することも課題とする。
In view of the above situation, it is an object of the present invention to provide a composition capable of imparting excellent antibacterial properties to a base material and having excellent adhesion of the antibacterial agent applied to the base material.

Another object of the present invention is to provide a modified base material, a wet wiper, and a spray.

　本発明者は、上記課題を解決すべく鋭意検討した結果、以下の構成により課題を解決できることを見出した。
As a result of earnest studies to solve the above problems, the present inventor has found that the problems can be solved by the following configurations.

（１）　抗菌剤と、シロキサン化合物とを含む、組成物。

（２）　抗菌剤が粒子状であり、

　抗菌剤の平均粒子径が１．０μｍ以下である、（１）に記載の組成物。

（３）　抗菌剤が、無機粒子と、無機粒子上に担持された有機系抗菌剤とを含む複合粒子である、（１）又は（２）に記載の組成物。

（４）　更に、溶媒を含み、

　溶媒が、実質的に水からなる、（１）～（３）のいずれかに記載の組成物。

（５）　シロキサン化合物が、後述する式（Ｘ）で表される化合物である、（１）～（４）のいずれかに記載の組成物。

（６）　更に、シランカップリング剤を含む、（１）～（５）のいずれかに記載の組成物。

（７）　基材と、基材上に配置された、（１）～（６）のいずれかに記載の組成物から形成される抗菌部とを有する、修飾基材。

（８）　基布と、基布に含浸させた（１）～（６）のいずれかに記載の組成物と、を有する、ウェットワイパー。

（９）　スプレー容器と、スプレー容器に収納された（１）～（６）のいずれかに記載の組成物と、を有するスプレー。
(1) A composition containing an antibacterial agent and a siloxane compound.

(2) The antibacterial agent is in the form of particles,

The composition according to (1), wherein the antibacterial agent has an average particle size of 1.0 μm or less.

(3) The composition according to (1) or (2), wherein the antibacterial agent is a composite particle containing inorganic particles and an organic antibacterial agent carried on the inorganic particles.

(4) Furthermore, including a solvent,

The composition according to any one of (1) to (3), wherein the solvent consists essentially of water.

(5) The composition according to any one of (1) to (4), wherein the siloxane compound is a compound represented by the formula (X) described below.

(6) The composition according to any one of (1) to (5), which further contains a silane coupling agent.

(7) A modified base material having a base material and an antibacterial part formed on the base material and formed of the composition according to any one of (1) to (6).

(8) A wet wiper comprising a base cloth and the composition according to any one of (1) to (6) impregnated into the base cloth.

(9) A spray comprising a spray container and the composition according to any one of (1) to (6) contained in the spray container.

　本発明によれば、基材に対して優れた抗菌性を付与でき、基材に付与された抗菌剤の固着性に優れる組成物を提供できる。

　また、本発明によれば、修飾基材、ウェットワイパー、及び、スプレーを提供できる。
ADVANTAGE OF THE INVENTION According to this invention, the composition which can provide the base material with the outstanding antibacterial property and is excellent in the adhesiveness of the antibacterial agent applied to the base material can be provided.

Moreover, according to this invention, a modified base material, a wet wiper, and a spray can be provided.

　以下、本発明について詳細に説明する。

　なお、本明細書における基（原子群）の表記において、置換、及び、無置換を記していない表記は、本発明の効果を損ねない範囲で、置換基を有さないものと共に置換基を有するものをも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。このことは、各化合物についても同義である。

　また、本明細書において、「（メタ）アクリレート」はアクリレート及び／又はメタクリレート（アクリレート及びメタクリレートのいずれか一方又は両方）を表し、「（メタ）アクリロイル」はアクリロイル及び／又はメタクリロイル（アクリロイル及びメタクリロイルのいずれか一方又は両方）を表す。

　また、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値、及び、上限値として含む範囲を意味する。
Hereinafter, the present invention will be described in detail.

In addition, in the description of the group (atom group) in the present specification, a description not showing substitution or non-substitution has a substituent together with a substituent having no substituent within a range not impairing the effect of the present invention. Also includes things. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This has the same meaning for each compound.

In addition, in the present specification, “(meth) acrylate” represents acrylate and / or methacrylate (either one or both of acrylate and methacrylate), and “(meth) acryloyl” means acryloyl and / or methacryloyl (of acryloyl and methacryloyl). Either one or both).

Further, in the present specification, a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.

　以下、本発明の組成物中に含まれる各種成分について詳述する。
Hereinafter, various components contained in the composition of the present invention will be described in detail.

＜抗菌剤＞

　抗菌剤としては、特に制限されず、公知の有機系抗菌剤及び／又は無機系抗菌剤が挙げられる。

　有機系抗菌剤としては、特に制限されず、例えば、フェノールエーテル誘導体、イミダゾール誘導体、スルホン誘導体、Ｎ－ハロアルキルチオ化合物、アニリド誘導体、ピロール誘導体、第４級アンモニウム化合物、ピリジン系化合物、トリアジン系化合物、ベンゾイソチアゾリン系化合物、及び、イソチアゾリン系化合物等が挙げられる。

　なお、有機系抗菌剤としては、天然系抗菌剤も含まれる。天然系抗菌剤としては、カニ及び／又はエビの甲殻等に含まれるキチンを加水分解して得られる塩基性多糖類のキトサンが挙げられる。
<Antibacterial agent>

The antibacterial agent is not particularly limited, and examples thereof include known organic antibacterial agents and / or inorganic antibacterial agents.

The organic antibacterial agent is not particularly limited, and examples thereof include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium compounds, pyridine compounds, triazine compounds, Examples thereof include benzoisothiazoline compounds and isothiazoline compounds.

Note that the organic antibacterial agent also includes a natural antibacterial agent. Examples of natural antibacterial agents include chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the shells of crabs and / or shrimps.

　無機系抗菌剤としては、特に制限されず、例えば、金属単体、金属イオン、金属を含む無機物、及び、無機担体と無機担体上に担持された金属又は有機系抗菌剤とを含む複合粒子が挙げられる。なお、複合粒子中に含まれる金属は、金属単体であっても、金属イオンであってもよい。

　無機系抗菌剤に含まれる金属の種類としては、特に制限されないが、銀、銅、亜鉛、水銀、鉄、鉛、ビスマス、チタン、錫、ジルコニウム、アルミニウム、及びニッケル等が挙げられ、なかでも、銀、銅、亜鉛、アルミニウム、又は、ジルコニウムが好ましく、銀、銅、亜鉛、又は、アルミニウムがより好ましく、銀又は銅が更に好ましく、銀が特に好ましい。

　金属を含む無機物としては、例えば、金属の酸化物、金属の窒化物、金属のハロゲン化物、金属のシアン化物、金属のセレン化物、金属の硫化物、金属のテルル化物、及び、金属の塩等が挙げられる。

　金属の塩としては、例えば、ヒ酸塩、フッ化水素塩、臭素酸塩、塩素酸塩、クロム酸塩、シアン酸塩、ヘキサフルオロアンチモン酸塩、ヘキサフルオロヒ酸塩、ヘキサフルオロリン酸塩、ヨウ素酸塩、イソチオシアン酸塩、モリブデン酸塩、硝酸塩、亜硝酸塩、過塩素酸塩、過マンガン酸塩、過レニウム酸塩、リン酸塩、セレン酸塩、亜セレン酸塩、硫酸塩、亜硫酸塩、テトラフルオロほう酸塩、テトラタングステン酸塩、チオシアン酸塩、及び、バナジン酸塩等が挙げられる。
The inorganic antibacterial agent is not particularly limited, and examples thereof include a metal simple substance, a metal ion, an inorganic substance containing a metal, and a composite particle containing an inorganic carrier and a metal or organic antibacterial agent supported on the inorganic carrier. Be done. The metal contained in the composite particles may be a simple metal or a metal ion.

The type of metal contained in the inorganic antibacterial agent is not particularly limited, and examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like. Silver, copper, zinc, aluminum or zirconium is preferable, silver, copper, zinc or aluminum is more preferable, silver or copper is further preferable, and silver is particularly preferable.

Examples of the inorganic substance containing a metal include a metal oxide, a metal nitride, a metal halide, a metal cyanide, a metal selenide, a metal sulfide, a metal telluride, and a metal salt. Is mentioned.

Examples of the metal salt include arsenate, hydrogen fluoride, bromate, chlorate, chromate, cyanate, hexafluoroantimonate, hexafluoroarsenate and hexafluorophosphate. , Iodate, isothiocyanate, molybdate, nitrate, nitrite, perchlorate, permanganate, perrhenate, phosphate, selenate, selenite, sulfate, sulfite Examples thereof include salts, tetrafluoroborates, tetratungstates, thiocyanates and vanadates.

　複合粒子中の無機担体の種類としては特に制限されないが、例えば、リン酸亜鉛カルシウム、リン酸カルシウム、リン酸ジルコニウム、リン酸アルミニウム、ケイ酸カルシウム、活性アルミナ、酸化ケイ素、ケイ酸塩ガラス、ホウケイ酸塩ガラス、リン酸塩ガラス、ゼオライト（結晶性アルミノケイサン塩）、アパタイト、ヒドロキシアパタイト、リン酸チタン、チタン酸カリウム、含水酸化ビスマス、含水酸化ジルコニウム、ハイドロタルサイト、及び、活性炭等が挙げられる。

　なお、酸化ケイ素（シリカ）としては、合成非晶質シリカが好ましい。合成非晶質シリカは、乾式法によって製造されるものと、湿式法によって製造されるものとに大別され、前者には乾式シリカがあり、後者には湿式シリカ、シリカゲル、及び、コロイダルシリカがあり、乾式シリカが好ましい。乾式シリカとしては、例えば、日本エアロジル株式会社より商品名アエロジルとして販売されているものが好ましく用いられる。
The type of inorganic carrier in the composite particles is not particularly limited, for example, zinc calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated alumina, silicon oxide, silicate glass, borosilicate. Examples thereof include glass, phosphate glass, zeolite (crystalline aluminosilicate salt), apatite, hydroxyapatite, titanium phosphate, potassium titanate, hydrous bismuth oxide, hydrous zirconium oxide, hydrotalcite, and activated carbon.

As the silicon oxide (silica), synthetic amorphous silica is preferable. Synthetic amorphous silica is roughly classified into those produced by a dry method and those produced by a wet method.The former includes dry silica, and the latter includes wet silica, silica gel, and colloidal silica. And dry silica is preferred. As the dry silica, for example, those sold under the trade name Aerosil by Nippon Aerosil Co., Ltd. are preferably used.

　無機担体としては、結晶性であっても、非晶性（アモルファス）であってもよいが、非晶性であることが好ましく、ガラスがより好ましい。ガラスを構成し得る材料としては、例えば、ケイ酸塩、ホウケイ酸塩、及び、リン酸塩等が挙げられる。ケイ酸塩としては、ケイ酸アルミニウムが好ましい。
The inorganic carrier may be crystalline or amorphous (amorphous), but is preferably amorphous and more preferably glass. Examples of materials that can form the glass include silicates, borosilicates, and phosphates. Aluminum silicate is preferable as the silicate.

　上記ケイ酸アルミニウムは、天然物又は合成物であってもよい。ケイ酸アルミニウムとしては、下記式（Ａ）で表される化合物が好ましい。

　Ａｌ２Ｏ３・ｎＳｉＯ２・ｍＨ２Ｏ    （Ａ）

　式（Ａ）におけるｎは６以上の正数（好ましくは、６～５０）であり、ｍは１～２０の正数である。なかでも、ｎが８～１５で、ｍが３～１５であることが好ましい。
The aluminum silicate may be a natural product or a synthetic product. As the aluminum silicate, a compound represented by the following formula (A) is preferable.

Al 2 O 3 · nSiO 2 · mH 2 O (A)

In the formula (A), n is a positive number of 6 or more (preferably 6 to 50), and m is a positive number of 1 to 20. Among them, it is preferable that n is 8 to 15 and m is 3 to 15.

　複合粒子に含まれる金属の種類としては、上述した無機系抗菌剤に含まれる金属の種類が挙げられる。

　複合粒子に含まれる有機系抗菌剤の種類としては、公知の有機系抗菌剤が挙げられ、例えば、上述した有機系抗菌剤の例示が挙げられる。なかでも、ヒドロキサム酸誘導体、第４級アンモニウム化合物、トリクロサン、又は、ジンク（Ｚｎ）ピリチオンが好ましい。

　ヒドロキサム酸誘導体としては、環状ヒドロキサム酸誘導体が挙げられ、より具体的には、１－ヒドロキシ－４－メチル－６－（２，４，４－トリメチルペンチル）－２（１Ｈ）－ピリドン　モノエタノールアミン塩（別名：ピロクトンエタノールアミン）、６－シクロヘキシル－１－ヒドロキシ－４－メチル－２（１Ｈ）－ピリドン、２－ヒドロキシエタンアミン、ピリドンカルボン酸系化合物（例えば、ピロミド酸、ピペミド酸 、シノキサシン）が挙げられる。

　第４級アンモニウム化合物としては、炭素数１～１８の長鎖アルキル基を有する第４級アンモニウム化合物が挙げられ、より具体的には、セチルリン酸ベンザルコニウム、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化メチルベンゼトニウム、塩化セチルピリジニウム、セトリモニウム、塩化ドファニウム、臭化テトラエチルアンモニウム、塩化ジデシルジメチルアンモニウム、及び、臭化ドミフェンが挙げられる。
Examples of the kind of metal contained in the composite particles include the kind of metal contained in the above-mentioned inorganic antibacterial agent.

Examples of the organic antibacterial agent contained in the composite particles include known organic antibacterial agents, and examples thereof include the above-mentioned organic antibacterial agents. Of these, hydroxamic acid derivatives, quaternary ammonium compounds, triclosan, and zinc (Zn) pyrithione are preferable.

Examples of the hydroxamic acid derivative include cyclic hydroxamic acid derivatives, and more specifically, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) -pyridone monoethanolamine Salts (also known as piroctone ethanolamine), 6-cyclohexyl-1-hydroxy-4-methyl-2 (1H) -pyridone, 2-hydroxyethanamine, pyridonecarboxylic acid compounds (eg, pyromidic acid, pipemidic acid, sinoxacin) ) Is mentioned.

Examples of the quaternary ammonium compound include quaternary ammonium compounds having a long-chain alkyl group having 1 to 18 carbon atoms, and more specifically, benzalkonium cetyl phosphate, benzalkonium chloride, benzethonium chloride, chloride Examples include methylbenzethonium, cetylpyridinium chloride, cetrimonium, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, and domiphen bromide.

　複合粒子としては、金属担持ゼオライト、金属担持アパタイト、金属担持ガラス、金属担持リン酸ジルコニウム、又は、金属担持ケイ酸カルシウムが好ましく、金属担持ガラスがより好ましい。
As the composite particles, metal-supported zeolite, metal-supported apatite, metal-supported glass, metal-supported zirconium phosphate, or metal-supported calcium silicate is preferable, and metal-supported glass is more preferable.

　抗菌剤が粒子状である場合、抗菌剤の平均粒子径は特に制限されないが、３．０μｍ以下の場合が多く、なかでも、１．０μｍ以下が好ましく、０．６μｍ以下がより好ましい。下限は特に制限されないが、０．０１μｍ以上の場合が多く、０．２μｍ以上の場合がより多い。
When the antibacterial agent is in the form of particles, the average particle diameter of the antibacterial agent is not particularly limited, but it is often 3.0 μm or less, preferably 1.0 μm or less, and more preferably 0.6 μm or less. Although the lower limit is not particularly limited, it is often 0.01 μm or more, and more often 0.2 μm or more.

　抗菌剤が粒子状である場合、平均粒子径は、電子顕微鏡を用いて観察することにより測定できる。具体的には、上記平均粒子径は、抗菌剤粒子について、一次粒子及び二次粒子（なお、「二次粒子」とは、一次粒子同士が融合あるいは接触して構成される集合体と定義する。）の直径を電子顕微鏡の画像から計測し、全粒子数の中の最も直径が小さい側の粒子数５％と、最も直径が大きい側の粒子数５％を除いた、９０％の範囲の粒子の直径を平均した値である。つまり、平均粒子径は、一次粒子及び二次粒子から求められる値である。また、直径とは、粒子の外接円相当直径のことをいう。

　なお、粒子の粒子形状に大きく違いがない場合、堀場製作所社製のレーザー回折／散乱式粒度分布測定装置を用いて５０％体積累積径（Ｄ５０）を３回測定して、３回測定した値の平均値を平均粒子径として代用してもよい。
When the antibacterial agent is in the form of particles, the average particle size can be measured by observing with an electron microscope. Specifically, the average particle diameter is defined as a primary particle and a secondary particle (the “secondary particle” is defined as an aggregate formed by fusing or contacting the primary particles with each other, with respect to the antibacterial agent particle. .) Diameter from the image of the electron microscope, and within the range of 90%, excluding 5% of the particles with the smallest diameter and 5% of the particles with the largest diameter of the total number of particles. It is a value obtained by averaging the diameters of the particles. That is, the average particle diameter is a value obtained from the primary particles and the secondary particles. Further, the diameter means a diameter corresponding to a circumscribing circle of particles.

In addition, when there is no significant difference in the particle shape of the particles, the 50% volume cumulative diameter (D50) is measured three times using a laser diffraction / scattering type particle size distribution measuring device manufactured by Horiba Ltd., and the value is measured three times. You may substitute the average value of the above as an average particle diameter.

　粒子状の抗菌剤の平均粒子径は、従来公知の方法により調節でき、例えば、乾式粉砕又は湿式粉砕を採用できる。乾式粉砕においては、例えば、乳鉢、ジェットミル、ハンマーミル、ピンミル、回転ミル、振動ミル、遊星ミル、及び、ビーズミル等が適宜用いられる。また、湿式粉砕においては、各種ボールミル、高速回転粉砕機、ジェットミル、ビーズミル、超音波ホモジナイザー、及び、高圧ホモジナイザー等が適宜用いられる。
The average particle size of the particulate antibacterial agent can be adjusted by a conventionally known method, and for example, dry pulverization or wet pulverization can be adopted. In the dry pulverization, for example, a mortar, jet mill, hammer mill, pin mill, rotary mill, vibration mill, planetary mill, bead mill, etc. are appropriately used. In wet pulverization, various ball mills, high-speed rotary pulverizers, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, etc. are used as appropriate.

　上記抗菌剤は公知の方法により製造でき、市販品を用いてもよい。
The above antibacterial agent can be produced by a known method, and a commercially available product may be used.

　抗菌剤は１種を単独で用いても、２種以上を併用してもよい。

　組成物中における抗菌剤の含有量（抗菌剤が複数含まれる場合はその合計含有量）は特に制限されないが、組成物の全固形分に対して、０．００１～５５質量％が好ましく、０．００１～５０質量％がより好ましく、０．０１～４０質量％が更に好ましい。
The antibacterial agents may be used alone or in combination of two or more kinds.

The content of the antibacterial agent in the composition (when a plurality of antibacterial agents are contained, the total content thereof) is not particularly limited, but is preferably 0.001 to 55% by mass with respect to the total solid content of the composition, and 0.001 to 50 mass% is more preferable, and 0.01 to 40 mass% is still more preferable.

＜シロキサン化合物＞

　シロキサン化合物とは、Ｓｉ－Ｏ－Ｓｉ結合を有する化合物である。

　シロキサン化合物としては、例えば、ケイ素原子に加水分解性基が結合した化合物の加水分解物、及び、その加水分解縮合物からなる群から選択される化合物が挙げられ、より具体的には、下記式（１）で表される化合物の加水分解物、及びその加水分解縮合物からなる群から選択される少なくとも１種が挙げられる。

式（１）　Ｓｉ－（ＯＲ）４

　上記式（１）中、Ｒは、炭素数１～４のアルキル基を表し、同一でも異なってもよい。
<Siloxane compound>

A siloxane compound is a compound having a Si-O-Si bond.

Examples of the siloxane compound include a hydrolyzate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a compound selected from the group consisting of hydrolyzed condensates, and more specifically, the following formulas At least one selected from the group consisting of a hydrolyzate of the compound represented by (1) and a hydrolyzed condensate thereof.

Formula (1) Si- (OR) 4

In the above formula (1), R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different.

　上記式（１）で表わされる化合物としては、テトラメチルシリケート、テトラエチルシリケート、テトラ－ｎ－プロピルシリケート、テトラ－ｉ－プロピルシリケート、テトラ－ｎ－ブチルシリケート、テトラ－ｉ－ブチルシリケート、テトラ－ｔ－ブチルシリケート、メチルエチルシリケート、メチルプロピルシリケート、メチルブチルシリケート、エチルプロピルシリケート、及び、プロピルブチルシリケート等が挙げられる。
Examples of the compound represented by the above formula (1) include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate and tetra-t. -Butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate, etc. are mentioned.

　式（１）で表される化合物の加水分解物とは、式（１）で表される化合物中のＯＲ基が加水分解して得られる化合物を意図する。なお、上記加水分解物は、ＯＲ基のすべてが加水分解されているもの（完全加水分解物）であっても、ＯＲ基の一部が加水分解されているもの（部分加水分解物）であってもよい。つまり、上記加水分解物は、完全加水分解物、若しくは、部分加水分解物、又はこれらの混合物であってもよい。

　また、式（１）で表される化合物の加水分解縮合物とは、式（１）で表される化合物中のＯＲ基が加水分解し、得られた加水分解物を縮合して得られる化合物を意図する。なお、上記加水分解縮合物としては、すべてのＯＲ基が加水分解され、かつ、加水分解物がすべて縮合されているもの（完全加水分解縮合物）であっても、一部のＯＲ基が加水分解され、一部の加水分解物が縮合しているもの（部分加水分解縮合物）であってもよい。つまり、上記加水分解縮合物は、完全加水分解縮合物、若しくは、部分加水分解縮合物、又はこれらの混合物であってもよい。
The hydrolyzate of the compound represented by the formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by the formula (1). The above-mentioned hydrolyzate is one in which all of the OR groups are hydrolyzed (complete hydrolyzate), but some of the OR groups is hydrolyzed (partial hydrolyzate). May be. That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.

Further, the hydrolytic condensate of the compound represented by the formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by the formula (1) and condensing the obtained hydrolyzate. Intended. As the hydrolysis-condensation product, even if all the OR groups are hydrolyzed and all the hydrolysis products are condensed (complete hydrolysis-condensation product), some of the OR groups are hydrolyzed. It may be decomposed and a part of the hydrolyzed product may be condensed (partial hydrolyzed condensate). That is, the hydrolysis-condensation product may be a complete hydrolysis-condensation product, a partial hydrolysis-condensation product, or a mixture thereof.

　シロキサン化合物としては、式（Ｘ）で表される化合物が好ましい。
As the siloxane compound, a compound represented by the formula (X) is preferable.

Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002

　ここで、式（Ｘ）中、Ｒ１～Ｒ４はそれぞれ独立に炭素数１～４のアルキル基を表す。また、ｎは２以上の整数を表す。

　ｎは、５以上の整数が好ましく、８以上の整数がより好ましい。上限は特に制限されないが、１００以下の整数が好ましく、２０以下の整数がより好ましい。
Here, in the formula (X), R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms. Further, n represents an integer of 2 or more.

n is preferably an integer of 5 or more, more preferably an integer of 8 or more. The upper limit is not particularly limited, but an integer of 100 or less is preferable, and an integer of 20 or less is more preferable.

　上記式（Ｘ）で表される化合物の市販品としては、例えば、コルコート社製「エチルシリケート４８」、「メチルシリケート５１」、「メチルシリケート５３Ａ」、及び、三菱化学社製「ＭＫＣシリケート　ＭＳ５１」「ＭＫＣシリケート　ＭＳ５６」「ＭＫＣシリケート　ＭＳ５７」等が挙げられる。

　なお、シロキサン化合物は１種を単独で用いても、２種以上を併用してもよい。
Examples of commercially available compounds represented by the above formula (X) include “Ethyl silicate 48”, “Methyl silicate 51”, “Methyl silicate 53A” manufactured by Colcoat, and “MKC silicate MS51” manufactured by Mitsubishi Chemical. Examples thereof include "MKC silicate MS56" and "MKC silicate MS57".

The siloxane compounds may be used alone or in combination of two or more.

　組成物中におけるシロキサン化合物の含有量としては特に制限されないが、組成物の全固形分に対して、２０～９９．８質量％が好ましく、２０～９０質量％がより好ましく、４０～９９質量％が更に好ましい。
The content of the siloxane compound in the composition is not particularly limited, but is preferably 20 to 99.8 mass%, more preferably 20 to 90 mass%, and more preferably 40 to 99 mass% with respect to the total solid content of the composition. Is more preferable.

＜その他の成分＞

　上記組成物は本発明の効果を奏する範囲内において、その他の成分を含んでいてもよい。
<Other ingredients>

The above composition may contain other components within the range in which the effects of the present invention are exhibited.

（溶媒）

　本発明の組成物は溶媒を含んでいてもよい。

　溶媒としては特に制限されず、水及び／又は有機溶媒が挙げられる。有機溶媒としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔｅｒｔ－ブタノール、ｎ－ペンタノール、イソペンタノール、フェニルエチルアルコール、カプリルアルコール、ラウリルアルコール、及び、ミリスチルアルコール等のアルコール系溶媒；メチルセロソルブ、エチルセロソルブ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピ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プロピルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノブチルエーテル、及び、ジプロピレングリコールモノブチルエーテル等のグリコールエーテル系溶媒；ベンゼン、トルエン、キシレン、及び、エチルベンゼン等の芳香族炭化水素系溶媒；シクロペンタン、シクロヘキサン、メチルシクロヘキサン、及び、エチルシクロヘキサン等の脂環族炭化水素系溶媒；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル、及び、ジ－ｎ－ブチルエーテル等のエーテル系溶媒；アセトン、メチルエチルケトン、及び、メチルイソブチルケトン等のケトン系溶媒；酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸ｎ－アミル、酢酸イソアミル、酢酸ヘキシル、プロピオン酸エチル、及び、プロピオン酸ブチル等のエステル系溶媒；１０％安息香酸デナトニウムアルコール溶液、ゲラニオール、八アセチル化ショ糖、ブルシン、リナロール、リナリールアセテート、及び、酢酸等の親水性溶媒；が挙げられる。
(solvent)

The composition of the present invention may include a solvent.

The solvent is not particularly limited, and examples thereof include water and / or an organic solvent. As the organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and , Alcohol solvents such as myristyl alcohol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Ethylene glycol monobutyl ether, diethylene glycol Glycol ether solvents such as nobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; cyclopentane, Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, and di-n-butyl ether; acetone, methyl ethyl ketone, and methyl isobutyl ketone Ketone-based solvent; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate Hexyl acetate, ethyl propionate, butyl propionate, and other ester solvents; 10% denatonium benzoate alcohol solution, geraniol, octaacetylated sucrose, brucine, linalool, linalyl acetate, and hydrophilicity of acetic acid A solvent;

　上記組成物中、粒状物の沈降を抑制する点、及び、形成される膜の消臭性がより優れる点で、アルコール系溶媒の含有量は、組成物全質量に対して、５質量％以上が好ましく、１０質量％以上が好ましい。上限値は特に制限されないが、例えば、９９質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下が更に好ましく、４５質量％以下が特に好ましい。
In the above composition, the content of the alcoholic solvent is 5% by mass or more based on the total mass of the composition, in that the sedimentation of the particulate matter is suppressed and the deodorant property of the formed film is more excellent. Is preferable and 10 mass% or more is preferable. The upper limit is not particularly limited, but for example, preferably 99% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 45% by mass or less.

　また、溶媒がアルコール系溶媒を含む場合、溶媒中におけるアルコールの含有量としては特に制限されないが、溶媒の全質量に対して、０．００１～１００質量％が好ましく、０．０１～９０質量％がより好ましく、５～９０質量％が更に好ましく、５～８０質量％が特に好ましい。
When the solvent contains an alcohol solvent, the content of the alcohol in the solvent is not particularly limited, but is preferably 0.001 to 100% by mass, and 0.01 to 90% by mass with respect to the total mass of the solvent. Is more preferable, 5 to 90% by mass is further preferable, and 5 to 80% by mass is particularly preferable.

　また、溶媒が、実質的に水からなることも好ましい。上記実質的とは、溶媒の全質量に対して、水の含有量が、９９質量％以上であることを意味し、９９．５質量％以上であることが好ましく、１００質量％であることがより好ましい。
It is also preferred that the solvent consists essentially of water. The above-mentioned "substantially" means that the content of water is 99% by mass or more, preferably 99.5% by mass or more, and preferably 100% by mass, with respect to the total mass of the solvent. More preferable.

　組成物中における溶媒の含有量としては特に制限されないが、組成物がより優れた塗布性を有する点で、組成物の固形分が、０．００１～８０質量％に調整されるのが好ましく、０．０１～１０質量％に調整されるのがより好ましく、０．１～５．０質量％に調整されるのが更に好ましい。

　溶媒は１種を単独で用いても、２種以上を併用してもよい。２種以上の溶媒を併用する場合、合計含有量が上記範囲内であることが好ましい。
The content of the solvent in the composition is not particularly limited, but the solid content of the composition is preferably adjusted to 0.001 to 80 mass% from the viewpoint that the composition has more excellent coatability. It is more preferably adjusted to 0.01 to 10% by mass, and further preferably adjusted to 0.1 to 5.0% by mass.

The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, the total content is preferably within the above range.

（シランカップリング剤）

　本発明の組成物はシランカップリング剤を含んでいてもよい。

　シランカップリング剤に含まれる官能基の種類は特に制限されないが、例えば、グリシジル基、アミノ基、ビニル基、（メタ）アクリロイル基、メルカプト基、及び、イソシアネート基が挙げられる。

　シランカップリング剤としては、式（Ｙ）で表される化合物が好ましい。

　式（Ｙ）　　Ｒ５－Ｌ－Ｓｉ（ＯＲ６）３

　Ｒ５は、グリシジル基、アミノ基、ビニル基、（メタ）アクリロイル基、メルカプト基、又は、イソシアネート基を表す。

　Ｌは、２価の連結基を表す。２価の連結基としては、アルキレン基、－ＮＨ－、－Ｏ－、－ＣＯ－、－ＣＯ2－、－Ｓ－、－ＳＯ3－、又は、これらを組み合わせた２価の基が挙げられる。

　Ｒ６は、アルキル基を表す。アルキル基の炭素数は特に制限されず、１～４が好ましく、１～２がより好ましい。
(Silane coupling agent)

The composition of the present invention may contain a silane coupling agent.

The type of functional group contained in the silane coupling agent is not particularly limited, and examples thereof include a glycidyl group, an amino group, a vinyl group, a (meth) acryloyl group, a mercapto group, and an isocyanate group.

As the silane coupling agent, a compound represented by the formula (Y) is preferable.

Formula (Y) R 5 -L-Si (OR 6 ) 3

R 5 represents a glycidyl group, an amino group, a vinyl group, a (meth) acryloyl group, a mercapto group, or an isocyanate group.

L represents a divalent linking group. Examples of the divalent linking group include an alkylene group, —NH—, —O—, —CO—, —CO 2 —, —S—, —SO 3 —, or a divalent group combining these. ..

R 6 represents an alkyl group. The carbon number of the alkyl group is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.

（分散剤）

　抗菌剤が粒子状である場合、上記組成物は、分散剤を含んでいてもよい。

　分散剤としては特に制限されず、公知の分散剤が使用できる。

　分散剤としては、ノニオン系又はアニオン系の分散剤が好ましく、カルボキシ基、リン酸基、及び水酸基等のアニオン性の極性基を有する分散剤（アニオン系分散剤）がより好ましい。

　アニオン系分散剤としては、市販品を使用できる。その具体例としては、ＢＹＫ社の商品名ＤＩＳＰＥＲＢＹＫ（登録商標）－１１０、－１１１、－１１６、－１４０、－１６１、－１６２、－１６３、１６４、－１７０、－１７１、－１７４、－１８０、－１８２、－１８５、及び、－２０２５等が好適に挙げられる。
(Dispersant)

When the antimicrobial agent is in particulate form, the composition may include a dispersant.

The dispersant is not particularly limited, and known dispersants can be used.

As the dispersant, a nonionic or anionic dispersant is preferable, and a dispersant having an anionic polar group such as a carboxy group, a phosphoric acid group, and a hydroxyl group (an anionic dispersant) is more preferable.

A commercial item can be used as an anionic dispersant. Specific examples thereof include trade names of BYK, DISPERBYK (registered trademark) -110, -111, -116, -140, -161, -162, -163, 164, -170, -171, -174, -180. , -182, -185, -2025 and the like are preferable.

　上記組成物中における分散剤の含有量としては特に制限されないが、組成物の全固形分に対して、例えば、７０質量％以下であり、５０質量％以下が好ましい。下限値は特に制限されないが、例えば、０．０１質量％以上であり、形成される膜の消臭性がより優れる点で、１．０質量％以上が好ましく、１５質量％以上が更に好ましい。

　分散剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の分散剤を併用する場合、合計含有量が上記範囲内であることが好ましい。
The content of the dispersant in the composition is not particularly limited, but is, for example, 70% by mass or less, and preferably 50% by mass or less, based on the total solid content of the composition. The lower limit is not particularly limited, but is, for example, 0.01% by mass or more, preferably 1.0% by mass or more, and more preferably 15% by mass or more from the viewpoint that the deodorant property of the formed film is more excellent.

The dispersants may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.

（触媒）

　組成物は、シロキサン化合物の縮合を促進する触媒（以下「反応触媒」ともいう。）を含んでいてもよい。
(catalyst)

The composition may include a catalyst that accelerates the condensation of the siloxane compound (hereinafter also referred to as “reaction catalyst”).

　触媒としては特に制限されないが、アルカリ触媒及び有機金属触媒等が挙げられる。

　アルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、及び、水酸化テトラメチルアンモニウム等が挙げられる。

　有機金属触媒としては、アルミニウムビス（エチルアセトアセテート）モノ（アセチルアセトネート）、アルミニウムトリス（アセチルアセトネート）、及び、アルミニウムエチルアセトアセテートジイソプロピレート等のアルミキレート化合物、ジルコニウムテトラキス（アセチルアセトネート）、及び、ジルコニウムビス（ブトキシ）ビス（アセチルアセトネート）等のジルコニウムキレート化合物、チタニウムテトラキス（アセチルアセトネート）、及び、チタニウムビス（ブトキシ）ビス（アセチルアセトネート）等のチタンキレート化合物、並びに、ジブチルスズジアセテート、ジブチルスズジラウレート、及び、ジブチルスズジオクチエート等の有機スズ化合物等が挙げられる。

　なかでも、より優れた本発明の効果を有する組成物が得られる点で、触媒としては、有機金属触媒が好ましく、なかでも、アルミキレート化合物、又はジルコニウムキレート化合物がより好ましく、アルミキレート化合物が更に好ましい。
The catalyst is not particularly limited, but examples thereof include an alkali catalyst and an organometallic catalyst.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.

Examples of the organic metal catalyst include aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate). And zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate), titanium tetrakis (acetylacetonate) and titanium chelate compounds such as titanium bis (butoxy) bis (acetylacetonate), and dibutyltin Examples of the organic tin compound such as diacetate, dibutyltin dilaurate, and dibutyltin dioctiate.

Among them, in terms of obtaining a composition having a more excellent effect of the present invention, the catalyst is preferably an organometallic catalyst, and among them, an aluminum chelate compound or a zirconium chelate compound is more preferable, and an aluminum chelate compound is further preferable. preferable.

　触媒の含有量は、組成物の全固形分１００質量部に対して、０．１～２０質量部が好ましく、０．２～１５質量部がより好ましく、０．３～１０質量部が更に好ましい。

　なお、触媒は１種を単独で用いても、２種以上を併用してもよい。２種以上の触媒を併用する場合、合計含有量が上記範囲内であることが好ましい。
The content of the catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and still more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition. ..

The catalyst may be used alone or in combination of two or more. When two or more catalysts are used in combination, the total content is preferably within the above range.

（界面活性剤）

　上記組成物は、界面活性剤を含んでいてもよい。界面活性剤は組成物の塗布性を向上する作用を有する。

　界面活性剤としては特に制限されず、例えば、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、及び、両性型界面活性剤等が挙げられる。

　界面活性剤の含有量としては、特に制限されないが、組成物の全固形分１００質量部に対して、０．０１質量部以上が好ましい。なお、界面活性剤の含有量の上限値は特に制限されないが、組成物の全固形分１００質量部に対して、１０質量部以下が好ましく、５質量部以下がより好ましく、４質量部以下が更に好ましい。

　なお、界面活性剤は１種を単独で用いても、２種以上を併用してもよい。２種以上を併用する場合は、それらの合計含有量が上記範囲内であることが好ましい。
(Surfactant)

The composition may include a surfactant. The surfactant has a function of improving the coating property of the composition.

The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

The content of the surfactant is not particularly limited, but is preferably 0.01 part by mass or more based on 100 parts by mass of the total solid content of the composition. The upper limit of the content of the surfactant is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 4 parts by mass or less with respect to 100 parts by mass of the total solid content of the composition. More preferable.

The surfactants may be used alone or in combination of two or more. When two or more kinds are used in combination, the total content thereof is preferably within the above range.

　ノニオン性界面活性剤としては、ポリエチレングリコールモノラウリルエーテル、ポリエチレングリコールモノステアリルエーテル、ポリエチレングリコールモノセチルエーテル、ポリエチレングリコールモノラウリルエステル、及び、ポリエチレングリコールモノステアリルエステル等が挙げられる。
Examples of the nonionic surfactant include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, and polyethylene glycol monostearyl ester.

　イオン性界面活性剤としては、アルキル硫酸塩、アルキルベンゼンスルホン酸塩、及び、アルキルリン酸塩等のアニオン性界面活性剤；アルキルトリメチルアンモニウム塩、及び、ジアルキルジメチルアンモニウム塩等のカチオン性界面活性剤；アルキルカルボキシベタイン等の両性型界面活性剤が挙げられる。
The ionic surfactants include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates and alkyl phosphates; cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts; Examples include amphoteric surfactants such as alkylcarboxybetaine.

（香料）

　上記組成物は、香料を含んでいてもよい。

　香料として、長谷川香料社製のフレーバーＨ－１、Ｈ－２、Ｈ－３、Ｈ－４、Ｈ－６、Ｈ－９、Ｈ－１０、Ｈ－１１、Ｈ－１２、Ｈ－１３、Ｈ－１４、高砂香料工業社製のフレーバーＴ－１００、Ｔ－１０１、Ｔ－１０２、Ｔ－１０３、Ｔ－１０４、Ｔ－１０５、Ｔ－１０６、Ｔ－１０７、ＥＤＡ－１７１、曽田香料社製フレーバーＳ－２０１、及び、理研香料工業社製フレーバーＤＡ－４０等が挙げられる。

　香料の含有量は、組成物の全質量に対して、０．０１～５質量％が好ましい。
(Fragrance)

The composition may include a fragrance.

As flavors, flavors H-1, H-2, H-3, H-4, H-6, H-9, H-10, H-11, H-12, H-13, H manufactured by Hasegawa Fragrance Co., Ltd. -14, flavors made by Takasago International Corporation T-100, T-101, T-102, T-103, T-104, T-105, T-106, T-107, EDA-171, Soda Aroma Co., Ltd. Flavor S-201, flavor DA-40 manufactured by Riken Fragrance Industry Co., Ltd. and the like can be mentioned.

The content of the fragrance is preferably 0.01 to 5 mass% with respect to the total mass of the composition.

　その他の成分としては、上記以外にも、造膜剤、消臭剤、紫外線吸収剤、防腐剤、ｐＨ調整剤、消泡剤、重合開始剤、触媒、光触媒性材料、充填剤、老化防止剤、帯電防止剤、難燃剤、接着性付与剤、レベリング剤、艶消し剤、光安定剤、染料、及び、顔料等の公知の添加剤が挙げられる。
In addition to the above, other components include film-forming agents, deodorants, ultraviolet absorbers, preservatives, pH adjusters, defoamers, polymerization initiators, catalysts, photocatalytic materials, fillers, antiaging agents. Well-known additives such as antistatic agents, flame retardants, adhesion promoters, leveling agents, matting agents, light stabilizers, dyes, and pigments can be used.

＜組成物のｐＨ＞

　上記組成物のｐＨは特に制限されないが、実使用環境で使用者の手荒れ等を考慮した場合、ｐＨを適切な範囲に調整することが好ましい。

　上記組成物のｐＨは、一般的に、２．０～１２．０が好ましく、３．０～１１．０がより好ましく、６．０～８．０が更に好ましい。

　なお、組成物のｐＨの調整方法としては、上記組成物に、酸若しくはアルカリを配合する方法が挙げられる。

　なお、ｐＨは、市販のｐＨ測定メータ（例えば、東亜ディーケーケー社製のｐＨメータ ＨＭ－３０Ｒ等）を用いて２５℃環境下にて測定できる。
<PH of composition>

The pH of the above composition is not particularly limited, but it is preferable to adjust the pH to an appropriate range in consideration of rough hands of the user in an actual use environment.

The pH of the above composition is generally preferably 2.0 to 12.0, more preferably 3.0 to 11.0, and even more preferably 6.0 to 8.0.

As a method of adjusting the pH of the composition, a method of adding an acid or an alkali to the above composition can be mentioned.

The pH can be measured in a 25 ° C. environment using a commercially available pH measuring meter (eg, pH meter HM-30R manufactured by Toa DKK Co., Ltd.).

＜組成物の粘度＞

　上記組成物の粘度は特に制限されず、用途に応じて調整すればよい。

　例えば、塗布性を向上させる場合又はスプレー等に適用する場合は、組成物の２５℃における粘度は、３００ｃＰ（センチポアズ：１ｃｐ＝１ｍＰａ・ｓ）以下が好ましく、２００ｃＰ以下がより好ましく、０．１～１５０ｃＰが更に好ましい。

　また、抗菌性及び消臭性の効果を長時間持続させる場合は、組成物の２５℃における粘度は、２５０ｃＰ以上が好ましく、３００ｃＰ以上がより好ましく、４００ｃＰ以上が更に好ましい。なお、その上限は、例えば、５００ｃＰ以下である。

　なお、粘度は、東機産業社製ＶＩＳＣＯＭＥＴＥＲ　ＴＵＢ－１０、又は、セコニック社製ＳＥＫＯＮＩＣ　ＶＩＳＣＯＭＥＴＥＲを用いて測定できる。
<Viscosity of composition>

The viscosity of the composition is not particularly limited and may be adjusted according to the application.

For example, when improving the coatability or applying it to a spray or the like, the viscosity of the composition at 25 ° C. is preferably 300 cP (centipoise: 1 cp = 1 mPa · s) or less, more preferably 200 cP or less, and 0.1- 150 cP is more preferable.

When the antibacterial and deodorant effects are maintained for a long time, the viscosity of the composition at 25 ° C. is preferably 250 cP or higher, more preferably 300 cP or higher, even more preferably 400 cP or higher. The upper limit is, for example, 500 cP or less.

The viscosity can be measured using Toki Sangyo Co., Ltd. VISCOMETER TUB-10 or Sekonic SEKONIC VISCOMETER.

＜組成物の製造方法＞

　上記組成物は、上述した必須成分及び任意成分を、適宜混合することによって調製できる。なお、上記成分の混合の順番は特に制限されない。
<Method for producing composition>

The composition can be prepared by appropriately mixing the above-mentioned essential components and optional components. The order of mixing the above components is not particularly limited.

＜組成物の用途＞

　上記組成物を基材に付与することにより、基材上に抗菌部を形成できる。つまり、基材と、基材上に配置された抗菌部とを有する修飾基材が得られる。

　なお、抗菌部とは、上述した組成物を用いて形成される部分を意味し、少なくとも抗菌剤とシロキサン化合物由来のバインダーとを含む。

　上記組成物を基材に付与する方法は特に制限されず、公知の塗布方法が挙げられ、例えば、スプレー、ロールコータ、グラビアコータ、スクリーン、スピンコータ、フローコータ、インクジェット、静電塗装、及び、ワイプ等が挙げられる。なかでも、スプレー、又は、ワイプが好ましい。

　ワイプの方法としては、上記組成物を不織布等の基布に含浸させ、その後、上記基布で基材の表面を拭く方法が挙げられる。
<Use of composition>

By applying the composition to a substrate, an antibacterial part can be formed on the substrate. That is, a modified base material having a base material and an antibacterial part arranged on the base material is obtained.

The antibacterial part means a part formed by using the composition described above, and contains at least an antibacterial agent and a binder derived from a siloxane compound.

The method of applying the composition to the substrate is not particularly limited, and known coating methods can be mentioned, for example, spray, roll coater, gravure coater, screen, spin coater, flow coater, inkjet, electrostatic coating, and wipe. Etc. Of these, spraying or wiping is preferable.

Examples of the wiping method include a method of impregnating a base cloth such as a non-woven fabric with the above composition and then wiping the surface of the base material with the above base cloth.

　なお、基材に組成物を付与した後、必要に応じて、基材上に付与された組成物に乾燥処理を施してもよい。乾燥処理としては、加熱処理が挙げられる。
After applying the composition to the substrate, the composition applied on the substrate may be subjected to a drying treatment, if necessary. Examples of the drying treatment include heat treatment.

　基材としては、抗菌部を支持する役割を果たせば、その種類は特に制限されない。

　基材の形状は特に制限されないが、板状、フィルム状、シート状、チューブ状、繊維状、繊維構造体状、及び、粒子状が挙げられる。なお、基材の形状が繊維構造体状とは、基材が不織布又は織物であるように、繊維から構成されるものであることを意味する。

　基材を構成する材料は特に制限されず、例えば、金属、ガラス、セラミックス、及び、プラスチック（樹脂）が挙げられる。なかでも、取り扱い性の点から、プラスチックが好ましい。プラスチックとしては、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン）、セルロース、ポリスチレン、ポリアミド、ポリイミド、及び、ポリ（メタ）アクリレート等が挙げられる。
The type of the base material is not particularly limited as long as it plays a role of supporting the antibacterial part.

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, a fiber structure shape, and a particle shape. In addition, that the shape of the base material is a fibrous structure means that the base material is composed of fibers such as a non-woven fabric or a woven fabric.

The material forming the base material is not particularly limited, and examples thereof include metal, glass, ceramics, and plastic (resin). Among them, plastic is preferable from the viewpoint of handleability. Examples of the plastic include polyolefin (polyethylene, polypropylene), cellulose, polystyrene, polyamide, polyimide, and poly (meth) acrylate.

　基材上に形成される抗菌部の配置位置は特に制限されず、基材全面を覆うように配置された膜状であっても、基材上に島状に点在して配置されていてもよい。

　抗菌部の膜厚は特に制限されないが、０．００１～５０μｍが好ましく、０．０１～１０μｍがより好ましい。

　なお、上記膜厚とは、膜の任意の１０点の位置における厚みを測定し、それらを算術平均した値を意図する。膜の厚みは、膜のサンプル片を樹脂に包埋して、ミクロトームで断面を削り出し、削り出した断面を走査電子顕微鏡で観察し測定する。
The position of the antibacterial part formed on the base material is not particularly limited, and even if it is a film-like structure arranged so as to cover the entire surface of the base material, it is arranged in a dotted pattern on the base material. Good.

The film thickness of the antibacterial part is not particularly limited, but is preferably 0.001 to 50 μm, more preferably 0.01 to 10 μm.

In addition, the said film thickness intends the value which measured the thickness in the position of arbitrary 10 points | pieces of a film | membrane, and arithmetically averaged them. The thickness of the film is measured by embedding a sample piece of the film in resin, shaving the cross section with a microtome, and observing the cut section with a scanning electron microscope.

＜ウェットワイパー＞

　本発明の実施形態に係るウェットワイパーは、基布と、上記基布に含浸させた組成物と、を有する。上記組成物は、既に説明したとおりである。
<Wet wiper>

A wet wiper according to an embodiment of the present invention includes a base cloth and a composition in which the base cloth is impregnated. The composition is as described above.

　上記基布としては、特に制限されず、天然繊維で形成されたものであっても、化学繊維で形成されたものであってもよい。

　天然繊維としては、例えば、パルプ、綿、麻、亜麻、羊毛、キヤメル、カシミヤ、モヘヤ、及び、絹等が挙げられる。

　化学繊維の材料としては、レーヨン、ポリノジック、アセテート、トリアセテート、ナイロン、ポリエステル、ポリアクリロニトリル、ポリビニルアルコール、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレン、ポリプロピレン、ポリウレタン、ポリアルキレンパラオキシベンゾエート、及び、ポリクラール等が挙げられる。

　なかでも、これらの基布のうち、組成物が含浸しやすい点で、親水性の基布が好ましい。親水性の基布とは、例えば、水酸基、アミノ基、カルボキシ基、アミド基、及び、スルホニル基等の親水性基を有する繊維を含む基布である。親水性の基布としては、具体的には、植物性繊維、綿、パルプ、動物性繊維、レーヨン、ナイロン、ポリエステル、ポリアクリロニトリル、及び、ポリビニルアルコール等が挙げられる。

　上記ウェットワイパーの基布としては、不織布、布、タオル、ガーゼ、及び、脱脂綿等を使用してもよく、不織布が好ましい。

　また、基布の目付（単位面積当たりの質量）は、１００ｇ／ｍ２以下が好ましい。上記組成物を基布に含浸させる際の含浸量は、基布の質量に対して１倍以上の量が好ましい。
The base cloth is not particularly limited, and may be formed of natural fibers or chemical fibers.

Examples of the natural fiber include pulp, cotton, hemp, flax, wool, quills, cashmere, mohair, and silk.

Examples of the chemical fiber material include rayon, polynosic, acetate, triacetate, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyalkylene paraoxybenzoate, and polyclar. Be done.

Among these, the hydrophilic base cloth is preferable among these base cloths because it is easily impregnated with the composition. The hydrophilic base cloth is, for example, a base cloth including fibers having a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amide group, and a sulfonyl group. Specific examples of the hydrophilic base cloth include vegetable fiber, cotton, pulp, animal fiber, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.

As the base cloth of the wet wiper, non-woven cloth, cloth, towel, gauze, absorbent cotton, etc. may be used, and non-woven cloth is preferable.

The basis weight (mass per unit area) of the base fabric is preferably 100 g / m 2 or less. The amount of impregnation when the above composition is impregnated into the base cloth is preferably at least 1 time the mass of the base cloth.

＜スプレー＞

　本発明の実施形態に係るスプレーは、スプレー容器と、上記スプレー容器に収納された組成物と、を有する。上記組成物は、既に説明したとおりである。

　本発明のスプレーとしては、上記組成物と噴射剤とを所定の容器に充填した形態が一例として挙げられる。用いられる噴射剤としては、特に制限されないが、例えば、液化石油ガス等が挙げられる。
<Spray>

The spray which concerns on embodiment of this invention has a spray container and the composition accommodated in the said spray container. The composition is as described above.

An example of the spray of the present invention is a form in which the above composition and a propellant are filled in a predetermined container. The propellant used is not particularly limited, but examples thereof include liquefied petroleum gas.

　また、本発明の組成物は、柔軟剤、洗剤、シャンプー、リンス等、消臭及び／又は抗菌が関係する製品に用いることができる。
Further, the composition of the present invention can be used for products such as softeners, detergents, shampoos, rinses, etc., which are related to deodorant and / or antibacterial.

　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により制限的に解釈されるべきものではない。
Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, and processing procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.

＜実施例１＞

　容器中でエタノール５６０ｇを攪拌しながら、純水１０ｇ、シロキサン化合物（三菱化学社製「ＭＫＣ（登録商標）シリケート」ＭＳ－５１」、式（Ｘ）で表される化合物に該当。ｎ＝５）５０ｇ、アルミキレートＤ（アルミニウムビス（エチルアセトアセテート）モノ（アセチルアセトネート）、エタノール希釈：固形分濃度１質量％）１５ｇ、ノニオン性界面活性剤（日本エマルジョン社製「エマレックス７１５」、純水希釈：固形分濃度０．５質量％）３０ｇ、アニオン性界面活性剤（ジ（２－エチルヘキシル）スルホコハク酸ナトリウム、純水希釈：固形分濃度０．２質量％）１０ｇ、シリカ粒子（日産化学工業社製「スノーテックスＯ－３３」、純水希釈：固形分濃度３３質量％）４０ｇ、分散剤（ＢＹＫ社製「ＤＩＳＰＥＲＢＹＫ（登録商標）－１８０」）３．６ｇを順次加えた後、平均粒子径を０．５μｍに制御した銀担持ガラス（富士ケミカル社製「バクテライトＭＰ－１０３ＤＶ」の平均粒子径を０．５μｍに制御したものに該当する。なお、富士ケミカル社製「バクテライトＭＰ－１０３ＤＶ」の無機担体はリン酸塩ガラスに該当する。）０．４８ｇを加えて、２０分間攪拌し、組成物１を得た。
<Example 1>

While stirring 560 g of ethanol in a container, 10 g of pure water, a siloxane compound (“MKC (registered trademark) silicate” MS-51 manufactured by Mitsubishi Chemical Corporation, corresponding to the compound represented by the formula (X), n = 5) 50 g, aluminum chelate D (aluminum bis (ethyl acetoacetate) mono (acetylacetonate), diluted with ethanol: solid content concentration 1% by mass) 15 g, nonionic surfactant (Nippon Emulsion "Emarex 715", pure water Dilution: solid content concentration 0.5% by mass) 30 g, anionic surfactant (sodium di (2-ethylhexyl) sulfosuccinate, pure water dilution: solid content concentration 0.2% by mass) 10 g, silica particles (Nissan Chemical Industry) "Snowtex O-33", diluted with pure water: solid content concentration of 33% by mass 40g, dispersant (BYK "DISPERBY" (Registered Trademark) -180 ") was sequentially added, and then the silver-supported glass (" Bacterite MP-103DV "manufactured by Fuji Chemical Co., Ltd.) having an average particle size of 0.5 μm. The inorganic carrier of "Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd. corresponds to phosphate glass.) 0.48 g was added and stirred for 20 minutes to prepare composition 1. Obtained.

（抗菌性評価）

　抗菌性評価用不織布（セルロース製）３×５ｃｍに対し、組成物１（０．２ｇ）とエタノール６０質量％の水溶液（０．８ｇ）との混合液を０．２ｇ噴霧し、１２時間、室温で乾燥してサンプルを作製した。得られたサンプルについて、ＪＩＳ Ｚ ２８０１記載の評価方法に準拠し、大腸菌を使用し、菌液への接触時間を３時間に変更して試験を実施した。試験後の抗菌活性値を測定し、以下の評価基準に基づいて評価を行なった。結果を第１表に示す。

「ＡＡ」：抗菌活性値が３．５以上

「Ａ」：抗菌活性値が３．０以上３．５未満

「Ｂ」：抗菌活性値が２．０以上３．０未満 

「Ｃ」：抗菌活性値が１．０以上２．０未満 

「Ｄ」：抗菌活性値が１．０未満 
(Antibacterial evaluation)

0.2 g of a mixed solution of the composition 1 (0.2 g) and an aqueous solution of 60% by mass of ethanol (0.8 g) was sprayed onto 3 x 5 cm of the non-woven fabric for evaluation of antibacterial property (cellulose), and the temperature was kept at room temperature for 12 hours. And dried to prepare a sample. The obtained sample was tested according to the evaluation method described in JIS Z 2801 by using Escherichia coli and changing the contact time with the bacterial solution to 3 hours. The antibacterial activity value after the test was measured and evaluated based on the following evaluation criteria. The results are shown in Table 1.

"AA": Antibacterial activity value is 3.5 or more

"A": Antibacterial activity value is 3.0 or more and less than 3.5

"B": Antibacterial activity value is 2.0 or more and less than 3.0

"C": Antibacterial activity value is 1.0 or more and less than 2.0

"D": Antibacterial activity value is less than 1.0

（固着性評価）

　抗菌性評価用不織布（セルロース製）３×５ｃｍに対し、組成物１（０．６ｇ）を噴霧して、１時間乾燥する処理を３回繰り返し（合計１．８ｇ噴霧）、その後、１２時間室温で乾燥して、サンプルを作製した。得られたサンプルを水１０ｇ中に浸漬して、１時間にわたって揺り動かす操作を実施した。その後、サンプルを取り出して、水に浸漬する前のサンプルに含まれる抗菌剤量を基準として、水から取り出したサンプルに含まれる抗菌剤の残存付着率を測定した。

「Ａ」：残存付着率が８５％以上

「Ｂ」：残存付着率が７０％以上８５％未満

「Ｃ」：残存付着率が５０％以上７０％未満

「Ｄ」：残存付着率が３０％以上５０％未満

「Ｅ」：残存付着率が３０％未満
(Evaluation of adhesion)

The composition 1 (0.6 g) was sprayed onto 3 x 5 cm of the antibacterial evaluation non-woven fabric (made of cellulose), and the treatment of drying for 1 hour was repeated 3 times (spraying 1.8 g in total), then for 12 hours at room temperature And dried to prepare a sample. The obtained sample was immersed in 10 g of water and shaken for 1 hour. Then, the sample was taken out, and the residual adherence rate of the antibacterial agent contained in the sample taken out from water was measured based on the amount of the antibacterial agent contained in the sample before being immersed in water.

"A": Residual adhesion rate is 85% or more

"B": Residual adhesion rate is 70% or more and less than 85%

"C": Residual adhesion rate is 50% or more and less than 70%

"D": Residual adhesion rate is 30% or more and less than 50%

"E": residual adhesion rate is less than 30%

＜実施例２～３３、比較例１～３＞

　後述する表１～表４に示すように、使用する組成物中の成分の種類、含有量等、並びに、（抗菌性評価）及び（固着性評価）で使用される不織布の基材の樹脂の種類等を変更した以外は、実施例１と同様の手順に従って、組成物２～３３を製造し、各種評価を実施した。

　なお、表１～表４に記載される記号は、以下を表す。

・銀抗菌剤（バクテライト）：富士ケミカル社製「バクテライトＭＰ－１０３ＤＶ」を表に記載の所定の粒子径に制御したもの

・銀抗菌剤（ノバロン）：銀担持リン酸ジルコニウム（東亞合成株式会社製「ノバロンＡＧ３００」）を表に記載の所定の粒子径に制御したもの

・銅抗菌剤（ＮＳ－２０Ｃ）：銅担持ケイ酸アルミニウムガラス（東亞合成株式会社製、「ケスモン（登録商標）ＮＳ－２０Ｃ」）

・シリカ＋塩化ベンゼルコニウム：特開２０１７－１０１０８４号公報の実施例１の手順にて製造したシリカ微粒子の表面にクラリアント社製の商品名オクトピロックス（登録商標、ピロクトンエタノールアミン）が付着している複合粒子

・シリカ＋Ｚｎピリチオン：特開２０１７－１０１０８４号公報の実施例１の手順を参照して製造した、シリカ微粒子の表面にＺｎピリチオンが付着している複合粒子

・ＭＳ－５６：シロキサン化合物（三菱ケミカル株式会社製「ＭＫＣ（登録商標）シリケート」ＭＳ－５６」、式（Ｘ）で表される化合物に該当。ｎ＝１０～１１）

・ＭＳ－５７：シロキサン化合物（三菱ケミカル株式会社製「ＭＫＣ（登録商標）シリケート」ＭＳ－５７」、式（Ｘ）で表される化合物に該当。ｎ＝１５～１８）

・メチルシリケート５１：シロキサン化合物（コルコート社製、式（Ｘ）で表される化合物に該当。ｎ＝４）

・メチルシリケート５３Ａ：シロキサン化合物（コルコート社製、式（Ｘ）で表される化合物に該当。ｎ＝７）

・ＫＢＭ４０３：３－グリシドキシプロピルトリエトキシシラン（信越化学工業株式会社製、シランカップリング剤）

・ＫＢＭ９０３：３－アミノプロピルトリメトキシシラン（信越化学工業株式会社製、シランカップリング剤）
<Examples 2-33, Comparative Examples 1-3>

As shown in Tables 1 to 4 described below, the types and contents of the components in the composition to be used, and the resin of the base material of the non-woven fabric used in (Evaluation of antibacterial property) and (Evaluation of adhesiveness) Compositions 2 to 33 were manufactured according to the same procedure as in Example 1 except that the kind and the like were changed, and various evaluations were performed.

The symbols shown in Tables 1 to 4 represent the following.

・ Silver antibacterial agent (Bacterite): "Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd., which is controlled to have a predetermined particle size described in the table.

Silver antibacterial agent (Novalon): silver-supported zirconium phosphate ("Tobaro Gosei Co., Ltd." Novalon AG300 ") controlled to a predetermined particle size shown in the table.

・ Copper antibacterial agent (NS-20C): Copper-supported aluminum silicate glass (manufactured by Toagosei Co., Ltd., "Kesmon (registered trademark) NS-20C")

Silica + benzelkonium chloride: Octopirox (registered trademark, piroctone ethanolamine) manufactured by Clariant Co., Ltd. adheres to the surface of the silica fine particles produced by the procedure of Example 1 of JP-A-2017-101084. Composite particles

Silica + Zn pyrithione: composite particles produced by referring to the procedure in Example 1 of JP-A-2017-101084 and having Zn pyrithione attached to the surface of silica fine particles.

MS-56: Siloxane compound (corresponds to the compound represented by the formula (X), “MKC (registered trademark) silicate MS-56” manufactured by Mitsubishi Chemical Corporation. N = 10 to 11)

MS-57: Siloxane compound (corresponds to the compound represented by the formula (X), “MKC (registered trademark) silicate” MS-57 manufactured by Mitsubishi Chemical Corporation. N = 15 to 18)

Methyl silicate 51: siloxane compound (corresponding to the compound represented by the formula (X), manufactured by Colcoat Co., Ltd., n = 4)

Methyl silicate 53A: siloxane compound (corresponding to the compound represented by the formula (X), manufactured by Colcoat Co., n = 7)

KBM403: 3-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., silane coupling agent)

KBM903: 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., silane coupling agent)

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

　上記のように、本発明の組成物１～３３を用いた場合、所望の効果が得られることが確認された。
As described above, it was confirmed that the desired effects were obtained when the compositions 1 to 33 of the present invention were used.

　続いて、組成物１～３３それぞれに対して、減圧処理を行い、組成物中のエタノールを留去した。その後、留去により減少した重量を水で置換し、溶媒中の水が９９質量％以上である組成物３４～６６を作成した。

　なお、得られた組成物中の水分が９９質量％以上であることは、ガスクロマトグラフィーを用いて、含まれるエタノールが１質量％以下であることにより確認した。
Subsequently, each of Compositions 1 to 33 was subjected to a reduced pressure treatment to distill off ethanol in the composition. Then, the weight reduced by distillation was replaced with water to prepare compositions 34 to 66 in which the water content in the solvent was 99% by mass or more.

The content of water in the obtained composition was 99% by mass or more, and it was confirmed by gas chromatography that the content of ethanol was 1% by mass or less.





　得られた組成物３４～６６のそれぞれに対し、実施例３４～６６として抗菌性評価と固着性評価を実施したところ、エタノールが含まれた組成物１～３３を使用した実施例１～３３それぞれと同じ評価結果が得られた。

　なお、抗菌性評価については、エタノール６０質量％の水溶液と混合させる工程を、純水との混合に変更した以外は同様に実施した。
Each of the obtained compositions 34 to 66 was subjected to antibacterial property evaluation and sticking property evaluation as Examples 34 to 66, and Examples 1 to 33 using Compositions 1 to 33 containing ethanol were respectively performed. The same evaluation result as was obtained.

The antibacterial property evaluation was performed in the same manner except that the step of mixing with an aqueous solution of 60% by mass of ethanol was changed to mixing with pure water.

　また、上述した実施例４で使用した組成物４中のエタノールを全て水に置き換えた組成物を調製して、実施例４で使用した組成物と共に、以下の親水性評価を実施した。

　実施例４で使用した組成物を用いた場合の評価は「Ｃ」であり、実施例４で使用した組成物中のエタノールを全て水に置き換えた組成物を用いた場合の評価は「Ａ」であった。
Further, a composition was prepared by replacing all the ethanol in the composition 4 used in Example 4 with water, and the following hydrophilicity evaluation was performed together with the composition used in Example 4.

The evaluation using the composition used in Example 4 is “C”, and the evaluation using the composition in which all the ethanol in the composition used in Example 4 is replaced with water is “A”. Met.

（親水性評価）

　抗菌性評価用不織布（セルロース製）３×５ｃｍに対し、組成物（０．２ｇ）を噴霧し、１２時間室温で乾燥してサンプルを作製した。得られたサンプルの組成物を噴霧した部分に、水２０μＬの液滴を９個滴下し、吸い込みの有無を評価した。以下の基準に従って評価した。

「Ａ」：９個吸い込む

「Ｂ」：６～８個吸い込む

「Ｃ」：３～５個吸い込む

「Ｄ」：０～２個吸い込む
(Hydrophilicity evaluation)

The composition (0.2 g) was sprayed onto 3 × 5 cm of the antibacterial evaluation non-woven fabric (made of cellulose) and dried at room temperature for 12 hours to prepare a sample. Nine droplets of 20 μL of water were dropped on the sprayed portion of the composition of the obtained sample, and the presence or absence of suction was evaluated. It evaluated according to the following criteria.

"A": Inhale 9

"B": Inhale 6-8 pieces

"C": Inhale 3 to 5 pieces

"D": Inhale 0 to 2

Claims (9)


  1. 　抗菌剤と、シロキサン化合物とを含む、組成物。
    A composition comprising an antibacterial agent and a siloxane compound.

  2. 　前記抗菌剤が粒子状であり、

    　前記抗菌剤の平均粒子径が１．０μｍ以下である、請求項１に記載の組成物。
    The antibacterial agent is particulate,

    The composition according to claim 1, wherein the average particle diameter of the antibacterial agent is 1.0 µm or less.

  3. 　前記抗菌剤が、無機粒子と、前記無機粒子上に担持された有機系抗菌剤とを含む複合粒子である、請求項１又は２に記載の組成物。
    The composition according to claim 1 or 2, wherein the antibacterial agent is a composite particle containing inorganic particles and an organic antibacterial agent carried on the inorganic particles.

  4. 　更に、溶媒を含み、

    　前記溶媒が、溶媒の全質量に対して、水の含有量が９９質量％以上である、請求項１～３のいずれか１項に記載の組成物。
    Furthermore, including a solvent,

    The composition according to any one of claims 1 to 3, wherein the solvent has a water content of 99% by mass or more based on the total mass of the solvent.

  5. 　前記シロキサン化合物が、式（Ｘ）で表される化合物である、請求項１～４のいずれか１項に記載の組成物。

    Figure JPOXMLDOC01-appb-C000001
    式（Ｘ）中、Ｒ１～Ｒ４はそれぞれ独立に炭素数１～４のアルキル基を表す。ｎは、８以上の整数を表す。
    The composition according to any one of claims 1 to 4, wherein the siloxane compound is a compound represented by the formula (X).

    Figure JPOXMLDOC01-appb-C000001
    In formula (X), R 1 to R 4 each independently represent an alkyl group having 1 to 4 carbon atoms. n represents an integer of 8 or more.

  6. 　更に、シランカップリング剤を含む、請求項１～５のいずれか１項に記載の組成物。
    The composition according to any one of claims 1 to 5, further comprising a silane coupling agent.

  7. 　基材と、前記基材上に配置された、請求項１～６のいずれか１項に記載の組成物から形成される抗菌部とを有する、修飾基材。
    A modified substrate having a substrate and an antibacterial portion formed from the composition according to any one of claims 1 to 6 disposed on the substrate.

  8. 　基布と、前記基布に含浸させた請求項１～６のいずれか１項に記載の組成物と、を有する、ウェットワイパー。
    A wet wiper comprising a base cloth and the composition according to claim 1 impregnated in the base cloth.

  9. 　スプレー容器と、前記スプレー容器に収納された請求項１～６のいずれか１項に記載の組成物と、を有するスプレー。
    A spray comprising a spray container and the composition according to any one of claims 1 to 6 contained in the spray container.
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WO2016186051A1 (en) * 2015-05-15 2016-11-24 富士フイルム株式会社 Antibacterial solution, antibacterial film and wet wipe
WO2017033926A1 (en) * 2015-08-25 2017-03-02 富士フイルム株式会社 Antibacterial solution, antibacterial film, spray and cloth
WO2017179383A1 (en) * 2016-04-13 2017-10-19 富士フイルム株式会社 Antibacterial composition, antibacterial film and wet wiper

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WO2016047568A1 (en) * 2014-09-22 2016-03-31 富士フイルム株式会社 Antibacterial sheet, antibacterial coat, laminated body, and antibacterial fluid
WO2016186051A1 (en) * 2015-05-15 2016-11-24 富士フイルム株式会社 Antibacterial solution, antibacterial film and wet wipe
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Publication number Priority date Publication date Assignee Title
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