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WO2008004677A1 - Composition antimicrobienne liquide capable de former des films transparents - Google Patents

Composition antimicrobienne liquide capable de former des films transparents Download PDF

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Publication number
WO2008004677A1
WO2008004677A1 PCT/JP2007/063609 JP2007063609W WO2008004677A1 WO 2008004677 A1 WO2008004677 A1 WO 2008004677A1 JP 2007063609 W JP2007063609 W JP 2007063609W WO 2008004677 A1 WO2008004677 A1 WO 2008004677A1
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WIPO (PCT)
Prior art keywords
group
transparent film
forming liquid
liquid antibacterial
composition according
Prior art date
Application number
PCT/JP2007/063609
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English (en)
Japanese (ja)
Inventor
Tetsuya Sahara
Yukiko Takahashi
Original Assignee
Nippon Soda Co., Ltd.
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Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to JP2008523766A priority Critical patent/JP5121025B2/ja
Publication of WO2008004677A1 publication Critical patent/WO2008004677A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24—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

Definitions

  • the present invention relates to a transparent film-forming liquid antibacterial agent composition, and more particularly to a transparent film-forming antibacterial agent composition excellent in transparency and durability of antibacterial effect.
  • Patent Document 1 includes a fungicidal effect of a fungicide by adding a dialkyldimethyl ammonium salt having a carbon chain length of 10 to 14 as a water repellent film forming component in addition to a fungicide component. It is described to improve sustainability. However, the sustainability of antibacterial agents was not sufficient.
  • thiabendazole which is often used as an antifungal agent, has low solubility in solvents such as alcohol and water, so even if it is simply dissolved in an appropriate solvent and sprayed, the solution is applied immediately. It was more difficult to obtain a continuous fungicidal effect because it precipitated in the water and became cloudy. In particular, for indoor use, precipitation and white turbidity of thiabendazole gave viewers the impression that cleanliness was impaired, so there was a problem in practical use.
  • Patent Document 2 it can be applied in a short time and economically to a building exterior member in which algae 'fungi have propagated and biological contamination has progressed, and biologically contaminated parts can be easily applied.
  • a water-based anti-algae (strength) paint that can be renovated into a water-based anti-algae (strength) coating for exterior parts of buildings with synthetic resin latex as the main component, 0. 01
  • Patent Document 2 describes that the paint can be made into a transparent coating film, but this can be achieved by reducing the thickness of the resin solids concentration and reducing the film thickness (paragraph number 0 of Patent Document 2). 031).
  • the film thickness after coating is not particularly limited, and can be 0.5 to 20 ⁇ m, preferably 1 to 15 ⁇ m. Since it is thinner than ⁇ 200 / ⁇ ), the difference between the transparent coating film portion and the other portions cannot be distinguished on the coated surface according to the present invention. ”(Patent Document 2) (Refer to the description of Step No. 0040) and “The concentration of the solids in the resin is less than 1% by weight.
  • Patent Document 2 it is desirable to make the film thickness as thin as possible.
  • the film thickness is 5 m or more, if it is used for a building exterior member like the paint of Patent Document 2 (see the description in paragraph No. 0034 of Patent Document 2), the transparency is sufficient.
  • the paint of Patent Document 2 cannot provide sufficient transparency for indoor use because it will be seen closer in the case of indoor use for mirrors and tile joints.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-230976
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-292868
  • An object of the present invention is to provide a transparent film-forming liquid antibacterial agent composition having a high transparency and a high persistence of transparency when applied to a subject with low irritation and a high durability of the antibacterial effect. There is something to do.
  • transparent film-forming liquid antibacterial agent composition is simply referred to as “antibacterial agent composition”.
  • the present inventors use transparent organic polymer having a hydrophobic site, an antibacterial component, and an alcohol-based solvent to achieve transparency that is excellent in transparency, durability of transparency, and durability of antibacterial effect. It has been found that a film can be obtained, and the present invention has been completed.
  • the present invention relates to the following inventions.
  • a transparent film-forming liquid antibacterial agent composition comprising an organic polymer having a hydrophobic site, an antibacterial component, and water or an alcohol solvent.
  • Nonpolar basic force Alkyl group, alkenyl group, fullyl group, condensed polycyclic phenyl group, and chain polycyclic phenyl group power are selected from any one or more selected.
  • the transparent film-forming liquid antibacterial composition according to any one of (1) to (3), wherein the organic polymer further has a hydrophilic site.
  • the transparent film formation according to (5) characterized in that it is one or two or more selected from the group force consisting of an acid group, a carboxylic acid group, an aluminate group, a nitrile group, and a thioalcohol group Liquid antibacterial composition.
  • Antifungal ingredients are thiabendazole, 3 odor-2 propargyl butyl carbamate, 1, 2 benzotriazoline 1-one, jodomethyl 1-p-tolylsulfone, 2, 3, 5, 6 (Methylsulfuryl) pyridine, and 1— (2- (2,4 Diclonal Methyl) 2- (2-Probeoxy) ethyl) 1H-imidazole (imazalyl) Power Group force selected Any 1 The transparent film-forming liquid antibacterial composition according to (11), wherein the composition is a seed or two or more kinds.
  • the transparent film-forming liquid antibacterial agent composition according to any one of (1) to (21), a transparent film-forming liquid antibacterial agent composition for windows, a transparent film-forming liquid antibacterial agent composition for kitchens, and a bathroom A method for use as a transparent film-forming liquid antibacterial agent composition.
  • a spray-type antibacterial agent wherein the transparent film-forming liquid antibacterial agent composition according to any one of (1) to (21) is contained in a container.
  • FIG. 1 is a diagram showing a 13 C-NMR chart of a styrene maleic anhydride copolymer (resin A).
  • FIG. 2 is a diagram showing a 13 C-NMR chart of styrene-maleic anhydride copolymer hydrolyzate (resin a).
  • FIG. 3 is a diagram showing IR ⁇ vector of rosin A.
  • FIG. 4 is a diagram showing the IR ⁇ vector of rosin a.
  • FIG. 5 is a diagram showing IR ⁇ vector of rosin B.
  • FIG. 6 is a diagram showing an IR ⁇ vector of rosin b.
  • FIG. 7 is a diagram showing IR ⁇ vector of rosin C.
  • FIG. 8 is a diagram showing the IR ⁇ vector of rosin c.
  • FIG. 9 is a diagram showing IR ⁇ vector of rosin D.
  • FIG. 10 is a diagram showing an IR ⁇ vector of rosin d.
  • FIG. 11 is a diagram showing an IR spectrum of rosin E.
  • FIG. 12 is a diagram showing IR ⁇ vector of rosin e.
  • FIG. 13 is a diagram showing IR ⁇ vector of rosin F.
  • FIG. 14 is a diagram showing the IR ⁇ vector of rosin f.
  • FIG. 15 is a diagram showing IR ⁇ vector of rosin G.
  • FIG. 16 shows an IR spectrum of rosin g.
  • the antibacterial agent composition of the present invention is not particularly limited as long as it contains an organic polymer having a hydrophobic site, an antibacterial component, and an alcohol solvent.
  • the organic polymer refers to an organic polymer having a hydrophobic site.
  • the hydrophobic site is not particularly limited, but examples thereof include alkyl groups; vinyl groups, vinylidene groups, alkenyl groups such as ethynyl groups; condensed polycyclic phenols such as phenyl groups, naphthyl groups, and anthral groups.
  • alkyl groups vinyl groups, vinylidene groups, alkenyl groups such as ethynyl groups
  • condensed polycyclic phenols such as phenyl groups, naphthyl groups, and anthral groups.
  • the following can be listed: a ru group; a chain polycyclic fur group such as a biphenyl group and a terfenyl group; and other nonpolar groups.
  • the organic polymer used in the present invention may not have a hydrophilic site, but from the viewpoint of superior transparency, durability of transparency, and durability of antibacterial effect, the hydrophilic polymer is further. It is preferable to have.
  • the hydrophilic site is not particularly limited, and examples thereof include a carboxyl group and a metal salt or an amine salt thereof; a sulfonic acid group and a metal salt or an amine salt thereof; a sulfoamide group; an amide group; an amino group; an imino group; a hydroxy group; Amino group; oxiamino group; diazo-um group; guanidine group; hydrazine group; phosphoric acid group; carboxylic acid group; aluminate group; -tolyl group; thioalcohol group; Among them, carboxyl group, sulfonic acid group, sulfoamide group, amide group, amino group, imino group, hydroxy group, quaternary amino group, oxyamino group, diazonium group, guanidine group, hydrazine group, phosphoric acid group, and caiic acid group , Aluminate group, nitrile group, and thioal
  • the organic polymer used in the present invention is a monomer having a hydrophilic portion. And a copolymer of one and a monomer having a hydrophobic part, and a polymer of a monomer having a hydrophilic part and a hydrophobic part.
  • a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part is: Preferred is a random copolymer of both monomers.
  • Examples of the monomer having a hydrophilic portion include mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, 2-atallylooxychetyl-2-hydroxyethyl phthalic acid, Monomers containing hydroxyl groups such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, monomers containing sulfonic groups such as sodium styrenesulfonate and sulfonated isoprene, acrylamide, methacryl Examples include amide compound monomers such as amides.
  • mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid can be preferably exemplified, and dicarboxylic acid monomers such as maleic acid and itaconic acid. More preferred It can be mentioned.
  • the monomer having a hydrophilic moiety used in the present invention may or may not have a hydrophilic moiety in the monomer state, and has a hydrophilic moiety in the state of the organic polymer contained in the antibacterial agent composition. It only has to be.
  • a maleic anhydride monomer does not have a hydrophilic site, but in the state of an organic polymer contained in the antibacterial agent composition, the anhydride group of maleic anhydride is opened by hydrolysis, resulting in a hydrophilic site. If a carboxyl group is generated, it is considered as an organic polymer having a hydrophilic portion.
  • a dicarboxylic acid monomer such as maleic acid or itaconic acid
  • Monomers having a hydrophobic site include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate.
  • Examples of the monomer having a hydrophilic part and a hydrophobic part include N-ethyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N-isopropyl (meth) atrylamide, N-n-propyl ( (Meth) acrylamide, N-methyl-N-ethyl (meth) atrylamide, N, N-jetyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl-N-n-propyl (meth) Acrylamide, N-Buylpyrrolidone, N-Vinylcaprolatatam, N-Isopropenylpyrrolidone, N-Isopropenylcap latatam, N- (Meth) atalyloylpyrrolidine, N- (Meth) atalyloylbiperidine I can list them.
  • the organic polymer used in the present invention include styrene maleic acid copolymers and derivatives thereof.
  • styrene maleic acid copolymer a compound having a ratio of styrene: maleic acid of 3: 1 to 1: 1 is preferably used, more preferably a compound of 2: 1, and particularly preferably a compound of 1: 1.
  • the styrene maleic acid copolymer derivative means a compound capable of inducing styrene maleic acid copolymer force and can be used in the present invention in the same manner as the styrene maleic acid copolymer.
  • the acid anhydride group of the maleic anhydride moiety is ring-opened to form a monoester Z monocarboxylic acid group or a styrene maleic acid copolymer.
  • a copolymer having a substituent such as a sulfonyl group at an appropriate position of the aromatic group a copolymer in which the maleic anhydride portion of the styrene maleic anhydride copolymer is imidized with amine, or a styrene maleic anhydride
  • examples include an ester group formed by ring opening of an acid anhydride group or a copolymer in which a carboxylic acid group is imidized with an amine.
  • a styrene maleic acid copolymer type (TG-750W: manufactured by Kyoeisha Co., Ltd.) (a maleic anhydride maleic anhydride polymer)
  • the acid anhydride group of the inic acid moiety is opened to form a monoester Z monocarboxylic acid group, a copolymer), SMA ester resin (manufactured by Sartoma Co., Ltd.) (styrene maleic anhydride polymer maleic anhydride) Copolymers in which the acid anhydride group of the acid moiety is opened to form a monoester Z monocarboxylic acid group), SMA resin: Ammonium salt aqueous solution (manufactured by Sartoma Co., Ltd.)
  • Preferred examples include copolymers in which the acid anhydride group of the maleic anhydride portion of the polymer is hydrolyzed to form a dicarboxylic acid group.
  • the molecular weight of the organic polymer is not particularly limited as long as the effects of the present invention can be obtained.
  • the number average molecular weight is preferably in the range of 1,000 to 100,000, and in the range of 2,000 to 20,000. More preferably, it is within.
  • the solubility of the organic polymer in water is preferably 5 to 5000 ppm, more preferably 10 to 20 OOppm! /.
  • the solubility of at least one organic polymer is 5 to 5000 ppm. More preferably, the weight percentage of the whole organic polymer is 30% or more.
  • Examples of the antibacterial component used in the present invention include known antifungal components, antibacterial components, antiyeast components, antiviral components, and the like.
  • the solubility in water is 0.2 g or less
  • the antibacterial component which has a solubility in a diol of 0.2 g or more, preferably 0.5 g or more and is solid at room temperature can be used after being dissolved.
  • solubility of antibacterial components in water and “solubility of antibacterial components in ethanol” refer to solubility in 100 g of water at 20 ° C and solubility in 100 g of ethanol at 20 ° C, respectively.
  • An antibacterial component having a solubility in water of not more than 0.2 gZl00 g and a solubility in ethanol of not less than 0.2 gZl00 g is more compatible with the organic polymer used in the present invention and can provide a highly transparent coating film. .
  • a fungicide component can be particularly preferably exemplified.
  • Antifungal agents that can be dissolved and used include thiabendazole (TBZ), 3- ododo 2-propargyl butyl carbamate, 1, 2-benzotriazolin-3-one.
  • antibacterial 'anti-yeast components 2, 4, 4' trichloro-2 'hydrated oxydiphenyl ether, 1, 2 benzothiazolone 3, N- (fluorochloromethylthio) phthalimide, 2, 4, 5, Specific examples thereof include 6-tetrachloro-isophthalonitrile and 1,3 bis (hydroxymethyl) -1,5'-dimethylhydantoin.
  • the solvent used in the present invention is preferably a strong alcohol solvent that is water or an alcohol solvent.
  • the alcohol-based solvent is not particularly limited as long as it is 100% alcohol or aqueous alcohol,. 20 to: L00 that hydroalcoholic containing alcohol weight 0/0 is good Mashigu 30-70 wt 0/0 it is water-containing alcohol containing alcohol more preferably a hydrous alcohol containing more preferred instrument 40-60 wt 0/0 alcohol. Further, the alcohol in the alcohol solvent may be one kind alone or may contain two or more kinds of alcohols. Ethanol is preferred as the alcohol in the alcohol solvent.
  • the antibacterial agent composition of the present invention is a film having a thickness of 20 to 300 nm formed by spray coating on a salted glass substrate, and the haze ratio after 24 hours from coating is preferably 5.0 or less, preferably 3.
  • An antibacterial agent composition having an organic polymer, an antibacterial component, and an alcohol-based solvent that is 3.0 or less, more preferably 2.0 or less.
  • the haze ratio in this specification was spray-coated on a 0.5 mm thick transparent salty vinyl sheet (manufactured by Atari Sunday, transparent rigid vinyl chloride board, haze ratio: 1.0 to 1.3). This is the value measured with a device made by Nippon Denshoku Industries Co., Ltd. after the coating film was dried at room temperature for 24 hours. If the haze ratio of the formed coating film is 5.0 or more, the coated surface is colored white and the aesthetic appearance is impaired. When such a coating film comes into contact with water, antibacterial components are eluted at an early stage. The effective period for maintaining the antibacterial effect is shortened.
  • the haze ratio is high.
  • the coating film is magnified and observed with a microscope, the antibacterial agent crystals are scattered as protrusions in the smooth coating film.
  • the coating film in which the sample is immersed in water for a certain period of time is used. It turns out that the crystal
  • the haze ratio is low, the coating film has a high haze ratio, and even if the ratio of the resin and the antibacterial agent is the same as that of the coating film, no antibacterial crystals are observed. The effect lasts for a long time.
  • the haze ratio is low, and the coating film has good compatibility between the resin and the antibacterial agent, so that the antibacterial agent is not separated and crystallized, and the resin and the antibacterial agent are uniformly dissolved.
  • the antibacterial effect lasts for a long time, but in the coating film with a high haze rate, the antibacterial agent and antibacterial agent are separated and the antibacterial agent forms a protruding crystal.
  • the crystallized antibacterial agent elutes early, and the concentration of the active ingredient in the coating film decreases, and the effective period of the antibacterial effect of the coating film is estimated to be shortened.
  • the content of the organic polymer in the antibacterial agent composition of the present invention is such that a 50% ethanol aqueous solution containing the organic polymer and 0.1% by weight of an antibacterial component is spray-coated on a vinyl chloride substrate.
  • the film having a thickness of 5 to 500 nm is not particularly limited as long as the haze ratio after 24 hours from application is 5.0 or less, but is 0.01 to 10% by weight with respect to the total amount of the antibacterial agent composition. More preferably, it can be in the range of 0.1 to 5% by weight, still more preferably 0.2 to 3% by weight, and more preferably 0.3 to 1% by weight.
  • the content ratio of the antibacterial component in the antibacterial agent composition of the present invention is such that a 50% ethanol aqueous solution containing the antibacterial component and 0.3% by weight of the organic polymer is sprayed onto a bull chloride substrate.
  • the haze ratio after coating for a film of 5 to 500 nm thickness formed after coating is 5.0 or less, but it is 0.01 to 10 weight with respect to the total amount of the antibacterial agent composition.
  • % More preferably 0.03 to 5% by weight, still more preferably 0.07 to 3% by weight, and even more preferably 0.1 to 1% by weight.
  • the above range of the content ratio of the antibacterial component is similarly applied when the antibacterial component is the above-described specific antibacterial component such as thiabendazole.
  • the mixing ratio of the organic polymer and the antibacterial component in the antibacterial agent composition of the present invention is such that a 50% ethanol aqueous solution containing the organic polymer and the antibacterial component is spray-applied to a vinyl chloride substrate.
  • the thickness ratio of the organic polymer to the antibacterial component is 1:50 to 50, as long as the haze ratio after coating for a film having a thickness of 5 to 500 nm is 5.0 or less. 1, more preferably 1:10 to: L0: 1, still more preferably 2: 1 to 5: 1, more preferably 2.5: 1 to 3.5: 1.
  • the antibacterial agent composition of the present invention has a haze ratio of 5.0 to 24 hours after application of a 5 to 500 nm thick film formed by spray-coating the antibacterial agent composition onto a salted glass substrate.
  • an optional component may be included in addition to the organic polymer having a hydrophobic site, the antibacterial component, and the alcohol solvent.
  • optional components include dispersion stabilizers, surfactants, water repellent components, organometallic compounds, amphiphilic metal oxide nanoparticles, and the like.
  • the antibacterial composition can be dissolved and dispersed more uniformly, which contributes to the sustainability of transparency and the sustainability of the antibacterial effect.
  • it further contains amphiphilic metal oxide nanoparticles when the antibacterial agent composition of the present invention is sprayed on a target, it has better transparency, transparency persistence, and antibacterial properties. Sustained effect is obtained.
  • the dispersion stabilizer refers to an agent such as a deflocculating agent, an anticoagulant such as a protective colloid having the effect of stably dispersing the dispersoid in the dispersion medium, such as glycolic acid, darconic acid, Polycarboxylic acids such as lactic acid, tartaric acid, citrate, malic acid and succinic acid; hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid; acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, Isopropyl acetate, n-butyl acetate, sec butyl acetate, t-butyl acetate, 2,4 hexanedione, 2,4 heptanedione, 3,5 heptanedione, 2,4 octanedione, 2,4 nonanedi
  • surfactant examples include surfactants such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, sulfosuccinates, amide ether sulfite types, sarcosine derivatives, phosphate ester types, stone wall types, and sulfonic acid types. Examples thereof include ionic surfactants.
  • cationic surfactant examples include cationic surfactants such as alkyl trimethyl ammonium salt, alkylamide amine type, alkyl dimethyl benzyl ammonium salt, and cationized polymer.
  • Nonionic surfactants include alkyl amide type: pegnol L 4, pegnol TH-8, pegnol L-9A, pegnol L 12S, pegnol L-20S, pegnol T-6, pegnol T-6 Gunol TE-10A, Pegnol ST-7, Pegnol ST-9, Pegnol ST-12, Pegnol 0-6A, Pegnol 0-107, Pegnol 0-16A, Pegnol 0-20, Pegnol Polyoxyethylene alkyls such as 0-24, Pegnol C-18, Pegnol S-4D, Pegnol HC-10 (manufactured by Toho Chemical Industry Co., Ltd.), Emargen 705, Emargen 707, Emargen 709 (manufactured by Kao Corporation) Ether
  • the water-repellent components include MegaFuck F-475 (Dainippon Ink Co., Ltd.), MegaFuck F-480SF (Dainippon Ink Co., Ltd.), MegaFuck F-470 (Dainippon Inkki).
  • Fluorine-based surfactants such as MegaFuck F-482 (Dainippon Ink Co., Ltd.), Dickguard F-90N (Dainippon Ink Co., Ltd.), Dickguard TE-5A (Dainippon) Fluorine fiber processing agents such as Ink Co., Ltd. and Dickguard F-445 (Dainippon Ink Co., Ltd.) can be suitably exemplified.
  • Preferable examples include methylpolysiloxane, dimethylsilicone oil, methylhydrogen silicone oil, modified silicone oil, and their emulsions.
  • organometallic compound examples include organometallic compounds containing, for example, titanium, zirconium oxide, aluminum, and silicon.
  • tetraisopropyl titanate, tetranormal butyl titanate, butynoretitanate dimer, tetra (2-ethylhexyl) titanate, tetramethinoretitanate, titanium acetylacetonate, titanium tetraacetyl acetate, Titanium ethyl acetate, titanium octanediolate, dihydroxybis (ammonium lactate) Titanium, titanium ratatoate, titanium triethanolamate, polyhydroxytitanium stearate, etc. can be preferably exemplified.
  • Particularly preferred are hydrophilic organometallic compounds such as titanium lactate.
  • amphiphilic metal oxide nanoparticles are not particularly limited as long as they have an affinity for both an aqueous solvent and an organic solvent, for example, hydrolysis. Examples thereof include hydrolysis products of metal compounds having a total of 2 or more functional groups and Z or hydroxyl groups, hydrolysis products of metal chelate compounds having 1 or more of total hydrolyzable groups and Z or hydroxyl groups, and the like.
  • amphiphilic metal oxide nanoparticles are added to the antibacterial agent composition of the present invention, when the film is formed using the composition, the hydrophobicity of the film is improved, and as a result, the water resistance of the film is improved. It is thought to improve.
  • the metal compound having two or more hydrolyzable groups and Z or hydroxyl groups in total is a metal compound having two or more hydrolyzable groups and Z or hydroxyl groups in total.
  • the hydrolyzable group is a functional group that hydrolyzes upon contact with water, or A functional group that can form a bond through a metal atom and an oxygen atom in the presence of water, specifically, a halogen atom, an amino group, an alkoxy group, an ester group, a carboxy group, a phosphoryl group, an isocyanate group. , Cyan group, epoxy group and the like.
  • the compound represented by Formula (I) can be illustrated preferably.
  • M represents a metal atom, preferably a metal atom of Group 13 to Group 15 of the periodic table, and more specifically, silicon, germanium, tin, lead, Titanium, zirconium, aluminum, indium, tantalum, tungsten, zinc, etc. can be exemplified, and among these, silicon, germanium, titanium, zirconium, and aluminum are more preferable.
  • R represents a hydrogen atom or an organic group which may have a hydrolyzable group capable of forming a bond via a metal atom and an oxygen atom.
  • the organic group that can be used include an alkyl group, an alkenyl group, and an aromatic group.
  • the carbon number of the organic group is not particularly limited, but is usually 1 to 20, preferably 1 to 12.
  • Specific examples of R include alkyl groups such as methyl, ethyl and propyl; chloromethyl, chloroethyl, chloropropyl, bromopropyl, bromooctyl and trifluoropropyl groups.
  • Halogenated alkyl groups such as: glycidoxypropyl group, epoxycyclohexyl group such as epoxycyclohexyl group; aminoalkyl groups such as aminoamino group, aminobutyl group; alkenyl groups such as buryl group, aryl group, etc .; And (meth) acryloxyalkyl groups such as xylpropyl group and methacryloxypropyl group; aralkyl groups such as benzyl group; aromatic groups such as phenyl group and naphthyl group;
  • X represents a hydrolyzable group or hydroxyl group bonded to M.
  • alkoxy having 1 to 12 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, etc.
  • a group containing a nitrogen atom such as a hydroxyimino group, a hydroxyamino group, an enoxy group, an amino group, or a strong rubamoyl group; a halogen atom such as a chlorine atom or a bromine atom; a hydroxyl group; Monkey.
  • Germanium alkoxides titanium alcohols such as tetra-n-propoxy titanium, tetra-isopropoxy titanium, tetra-n-butoxy titanium, tetra-sec butoxy titanium, tetra-butoxy titanium
  • Zirconium alkoxides such as tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetra-sec butoxyzirconium, tetra-t-butoxyzirconium; triethoxyaluminum, tri- n -propoxyaluminum , Triisopropoxyaluminum, tri-n-butoxyaluminum, trisec butoxyaluminum, tri-butoxyaluminum and other aluminum alkoxides; tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, benzyltrichlorosi
  • silane compounds such as butylmethylbis (methylethylketoximine) silane; 3, 3, 3-trifluoropropyl methoxydimethoxyhydroxysilane, 3, 3, 3-trifluoropropylmethoxydihydroxysilane, otachinole And hydroxysilanes such as ethoxydihydroxysilane.
  • metal alkoxides such as silane alkoxide, germanium alkoxide, titanium alkoxide, zirconium alkoxide, and aluminum alkoxide are preferable, and silane alkoxide, titanium alkoxide, and zirconium alkoxide are more preferable.
  • the above-mentioned metal chelate compound having one or more hydrolyzable groups and one or more Z or hydroxyl groups has one or more hydrolyzable groups and one or more Z or hydroxyl groups, and the chelate compound is bonded.
  • the hydrolyzable group is not particularly limited as long as it can be hydrolyzed to produce amphiphilic metal oxide nanoparticles. Examples of the hydrolyzable group include the hydrolyzable group and In the case of metal compounds having a total of two or more Z or hydroxyl groups, the same examples can be mentioned.
  • Examples of chelate compounds include j8-ketoesters such as methyl acetoacetate, ethyl acetoacetate, acetoacetate n-propyl, acetoacetate isopropyl, acetoacetate-n-butyl, acetoacetate-sec butyl, acetoacetate tbutyl Acetylacetone, hexane 2,4-dione, heptane 2,4 dione, heptane 3,5 dione, octane 2,4 dione, nonane 1,2,4 dione, 5-methyl-hexane 1,2,4 dione, etc.
  • j8-ketoesters such as methyl acetoacetate, ethyl acetoacetate, acetoacetate n-propyl, acetoacetate isopropyl, acetoacetate-n-butyl, acetoacetate-sec butyl, acetoacetate tbutyl Acety
  • J8-diketons oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other saturated aliphatic dicarboxylic acids; ethylene glycol and other glycols; oxyacetic acid Glycolic acids such as ethylenediamine tetraacetic acid (EDTA) and its sodium salt, ethylenediamine, 1,3 propanediamin, diethyl Nitrogen-containing compounds such as lentriamin, pentamethyljetylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridyl-methyl) amine; , Nicotinic acid, isonicotinic acid, phenanthorin, diphenantorin, substituted phenantorin, 2, 2 ', 6', 2, monoterpyridine, pyridineimine
  • a metal chelate compound having a total of 1 or more hydrolyzable group and Z or hydroxyl group diethoxybisacetinoreacetonate titanium, diisopropoxybisacetinoreacetonate titanium, dinormalpropoxybisacetylene Setonate Titanium, Dinormal Butoxy Bisacetylacetonate Titanium, Diethoxybisacetyl Casetonate Zirconium, Diisopropoxybiscetinoreacetonate Zinoreconium, Dinoremanole Propoxybis Acetylacetonate Zirconium, Di-N-Butoxybisacetyl cetate tozyl corn, Jetoxy cetinoreacetonato anoreminium, Diisopropoxy cetinorea Setonate Aluminum, Di-N-propoxy cetylacetonate Aluminum, Dinormal Butoxyacetyl acetonate aluminum, ethoxy bis (acetyl cetate) aluminum, isopropoxy bis (acetyl cetton
  • the metal chelate compound having one or more hydrolyzable groups and Z or hydroxyl groups in total includes, for example, a predetermined amount of a chelate compound in a metal compound having one or more hydrolyzable groups and Z or hydroxyl groups in total. It can obtain by adding and stirring. The resulting metal-cleared toy compound can be isolated, but can be used in the subsequent hydrolysis and polycondensation reaction as it is.
  • the hydrolysis product is a group consisting of a metal compound having a total of 2 or more hydrolyzable groups and Z or hydroxyl groups, and a metal chelate compound having a total of 1 or more hydrolyzable groups and Z or hydroxyl groups.
  • Hydrolysis with 1 mol or more, preferably 5 mol or more, more preferably 10 mol or more of water with respect to 1 mol of at least one selected (hereinafter collectively referred to as “metal compound etc.”).
  • the hydrolysis product may be a complete hydrolysis product or a partial hydrolysis product.
  • a hydrolysis product of a metal chelate compound having a total of 1 or more hydrolyzable groups and Z or hydroxyl groups is particularly preferred.
  • a metal chelate compound is dropped into water and hydrolyzed and mixed with an alcohol solution of an antibacterial component to obtain an antifungal solution, and 2) a metal chelate compound is added to an alcohol solvent. Then, water is added to hydrolyze, and then mixed with the alcohol solution of the antibacterial component to obtain an antifungal solution.
  • the method described in 3) is particularly preferred, and the preparation is preferably carried out at 0 ° C to room temperature.
  • an alcohol solvent such as ethanol or propanol is preferable.
  • an acid, a base and Z or a dispersion stabilizer may be added when hydrolyzing with water or after hydrolysis.
  • acids to be added include mineral acids such as hydrochloric acid, nitric acid, boric acid and borohydrofluoric acid, organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • a photoacid generator that generates an acid upon irradiation with light such as diphenyl-sulfo-hexoxano-reno-oral phosphate and triphenylenophospho-hexafluorophosphate; Examples include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, and phosphine.
  • the particle size of the amphiphilic metal oxide nanoparticles is 0.8 ⁇ ! ⁇ 100nm, preferably 1 ⁇ ! ⁇ 30nm, more preferably 3 ⁇ ! -LOnm nanoparticle strength Excellent dispersibility, can form a thin film with a thickness of 20-50 nm, and when used in combination with antibacterial components, forms a uniform mixture with antibacterial components, etc. Is preferable in that it precipitates as fine particles and does not precipitate into large crystals.
  • the amphiphilic metal oxide nanoparticles are preferable in that they can form nanoparticles with a uniform particle size of amphiphilic acid titanium nanoparticles.
  • the content of the metal oxide nanoparticles is 0.01 to 10 with respect to the total amount of the antibacterial agent composition. % By weight, particularly 0.1 to 2% by weight, is preferable for forming a transparent and flexible thin film.
  • the content of the antibacterial component is the content of metal oxide nanoparticles such as titanium oxide nanoparticles. (Weight) is 0.01-5 times, especially 0.1-2 times, such as antibacterial components and acid titanium nanoparticles It is preferable at the point which can form a uniform mixture with a metal oxide nanoparticle.
  • the antibacterial agent composition of the present invention is used for rubber packing of windows; ceilings in bathrooms, wall surfaces, drain outlets, tile joints; washstands; If it is the method of apply
  • the antibacterial agent composition of the present invention is a composition containing a antibacterial agent as an active ingredient, the rubber packing of the window; the ceiling of the bathroom, the wall surface, the vicinity of the drainage, the joint of the tile; It is used for the purpose of preventing the occurrence of mold by applying it to the place where it tends to grow.
  • a composition containing an antibacterial 'anti-yeast agent' as an active ingredient it is applied to the toilet floor and walls and the inner and outer wall surfaces of the toilet to prevent the scattered urine from decaying and generating odors.
  • it can be applied to the floor around the garbage collection area to prevent the liquid flowing out from the garbage from decaying and producing odors. It is used for the purpose of
  • the spray spraying method is preferable.
  • the thickness of the film formed by the antibacterial agent composition of the present invention is not particularly limited, but can be preferably in the range of 5 to 500 nm, more preferably in the range of 20 to 300 nm.
  • the spray-type antibacterial agent of the present invention is not particularly limited as long as the antibacterial agent composition of the present invention is contained in a container, and the container is not particularly limited as long as it can spray contents. Not limited to.
  • the reaction was performed at ° C for 6 hours.
  • the reaction solution was allowed to cool, reprecipitated with THF-methanol solvent, and dried to obtain 39.03 g of a styrene maleic anhydride copolymer.
  • the recovery rate was 87%.
  • the molecular weight of the obtained polymer was measured by GPC.
  • GPC used THF as a solvent and polystyrene as a standard substance. As a result, the number average molecular weight was 11,000, the weight average molecular weight was 82000, and the main peak was 19000. This rosin is hereinafter referred to as “Resin A”.
  • the fat A and the fat a obtained in the above (1) and (2) were analyzed by 13 C-NMR (single pulse decoupled without NOE method). It was confirmed that the copolymer yarn ratio of styrene and maleic anhydride in a was 1: 1, and that there was no unreacted maleic anhydride site in resin a.
  • Fig. 1 shows the 13 C-NMR chart of rosin A
  • Fig. 2 shows the 13 C-NMR chart of rosin a
  • Figure 3 shows the IR ⁇ vector of rosin A
  • Figure 4 shows the IR ⁇ vector of rosin a.
  • compositions having the compositions shown in Examples 1-2 and Comparative Example 1 in Table 1 below were prepared.
  • the compositions shown in Examples 1-2 and Comparative Example 1 were prepared by adding and mixing components other than the ethanol aqueous solution in the ethanol aqueous solution and stirring for 30 minutes or more.
  • a commercial product from AP was used for Comparative Example 1.
  • PAA Polyacrylic acid
  • a vinyl chloride substrate (made by Atari Sunday, transparent hard vinyl chloride plate, thickness 0.5mm, haze ratio 1.0 to 1.3) is prepared, and a bar coater (automatic coating equipment PI-1210 and ROD The composition of Example 1 was applied onto the vinyl chloride substrate using No. 5 bar (manufactured by Tester Sangyo Co., Ltd.). Various evaluations were performed using the samples formed by drying at room temperature for 24 hours after coating as film formation samples.
  • Example 2 The same operation was carried out using the composition of Example 2 and Comparative Example 1 in place of the composition of Example 1, and a film-forming sample was obtained for each.
  • Mold prevention test A film sample obtained by the same method as in 2 above was cut into a size of 3 cm ⁇ 7.5 cm to obtain a test piece. 50 ml of ion exchange water was put into the petri dish, and the test piece was immersed in the petri dish for a predetermined time (0, 1, 5, 10, 20, 40, 60 minutes) shown in Table 3. After soaking, it was dried at room temperature for 24 hours. Then, the presence or absence of mold on the surface of the test piece was evaluated in four stages. The results are shown in Table 3.
  • a contact angle was measured using water droplets.
  • the contact angle was measured with a contact angle meter (“Drop Master 700” manufactured by Kyowa Interface Science Co., Ltd.).
  • Table 4 shows the measured contact angles for each film sample. From this result, it was found that the film forming sample strength with a 3: 1 ratio of resin a: TBZ showed the highest hydrophobicity.
  • the contact angle of the salt-metal substrate as a blank was measured and found to be 65.8 °.
  • the number of carboxyl groups of rosin a is excessive with respect to TBZ1 molecules (TBZ1 with respect to carboxylic group 6 in molar ratio) even if rosin a: TBZ 3: 1. It is considered that this excess carboxyl group contributes to hydrophilization as the addition amount of is increased.
  • Resin B 2800 4500 4400 1/1 Resin C 2800 5000 4800 1/1 Resin D 4300 10000 8800 1/1 Resin E 23000 1 34000 53000 1/1 Resin F 30000 217000 58000 1/1 Resin G 3200 5900 5500 2/1
  • Commercially available resins B to G were hydrolyzed in the same manner as in Example A to obtain styrene maleic acid copolymers. The progress of hydrolysis was confirmed by IR spectrum. Table 6 shows the charge, yield, and yield of each. Each IR spectrum is shown in Figs.
  • compositions having the compositions shown in Examples 3 to 12 and Comparative Examples 2 and 3 in Table 7 below were prepared. The production method was carried out in the same manner as in Example A, and it was again prepared in Example 2.
  • composition of each example and comparative example is water.
  • Example 3 to 12 Samples of Examples 3 to 12, Example 2, and Comparative Examples 2 and 3 were prepared from a salty vinyl substrate (manufactured by Akrisande, transparent rigid vinyl chloride plate, thickness 0.5 mm, haze ratio 1.0 to 1). 3) was prepared, and the bull chloride substrate was placed vertically on the ground and applied with a commercially available spray bottle from a distance of 20 cm. Various types of evaluations were performed using samples formed by drying at room temperature for 24 hours after coating, as film formation samples.
  • a salty vinyl substrate manufactured by Akrisande, transparent rigid vinyl chloride plate, thickness 0.5 mm, haze ratio 1.0 to 1).
  • Table 8 shows the results of measuring the haze ratio of the above samples using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • a film sample obtained by the above method was cut into a size of 3 ⁇ 7.5 cm to obtain a test piece.
  • 20 mL of ion-exchanged water was put in the petri dish, and the test piece was immersed in the petri dish for a predetermined time described in Table 9.
  • the test piece was taken out every 2 hours and ion-exchanged water was exchanged. After immersion, it was dried at room temperature for 24 hours. Thereafter, a 3 ⁇ 3 cm cut sample was placed on an agar medium, and a black mold fungal spore suspension was spray-coated, and the presence or absence of force on the surface of the test piece was evaluated in four stages.
  • Example 1 2 Satoshi Satoshi Satoshi Comparative Example 2 ⁇ ⁇ + + + + + + + + + Comparative Example 3 ⁇ Ten + + + + +
  • Molds were grown on the entire surface, and the actual mold-proofing performance was evaluated in bathrooms with water-borne paint walls.
  • Test place Water-based paint wall bathroom (Niigata Prefecture)
  • Mold was removed from the wall surface of the water-borne paint, which was moldy, with a sodium hypochlorite mold remover. Showered and dried for 1 hour. The drug was then sprayed into the following four compartments. The size of one section is vertical lmX horizontal 0.5m. Dry for 3 hours. After that, using the bathroom as usual, we observed the occurrence of mold. The results are shown in Table 11. Sample No. 1 Blank... As it is, without applying a protective agent
  • 2, 4, 4, 1-trichloro-2, 1-hydroxydiphenyl ether and 1,2-benzothiazolone 3 are antibacterial and anti-yeast components.
  • compositions of Examples 13 and 14 were formed by the same method as Example B.
  • the haze ratio was measured by the same method as in Example B. Table 12 shows the measurement results.
  • the antibacterial agent composition of the present invention has high transparency and transparency when applied to a subject with low irritation and high antibacterial effect.

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Abstract

L'invention concerne une composition antimicrobienne liquide, ladite composition étant faiblement irritante et permettant d'obtenir un film transparent présentant une grande transparence, une grande persistance de la transparence et une grande persistance de l'activité antimicrobienne lorsqu'elle est pulvérisée sur un objet à traiter. La composition est caractérisée en ce qu'elle comprend un polymère organique comportant une fonction hydrophobe, un composant antimicrobien et de l'eau ou un solvant alcoolique. La fonction hydrophobe est de préférence un groupement non polaire, plus spécifiquement un ou plusieurs éléments choisis dans le groupe comprenant alkyle, alcényle, phényle, phényle polycyclique fusionné et phényle polycyclique en chaîne.
PCT/JP2007/063609 2006-07-07 2007-07-06 Composition antimicrobienne liquide capable de former des films transparents WO2008004677A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010275196A (ja) * 2009-05-26 2010-12-09 Nippon Soda Co Ltd 透明膜形成液状抗菌剤組成物
WO2011074188A1 (fr) * 2009-12-15 2011-06-23 日本曹達株式会社 Composition liquide transparente antimicrobienne à formation de film
JP2018538298A (ja) * 2015-12-10 2018-12-27 アダマ・マクテシム・リミテッド 高分子電解質層形成ブロックコポリマーならびにその組成物および使用
JP2020200299A (ja) * 2019-06-10 2020-12-17 三井化学株式会社 易洗浄の衛生材料または生活用品、および微生物の除去方法
WO2024034649A1 (fr) * 2022-08-10 2024-02-15 積水化学工業株式会社 Agent inhibiteur d'infection virale, composition de résine, et produit inhibiteur d'infection virale

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KR101961366B1 (ko) * 2018-06-25 2019-03-25 (주) 아이나노 금 나노 입자가 분산 함유되어 있는 항균제 혹은 소취제 조성물, 및 이를 함유한 금나노 함유 제품

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JPH10251565A (ja) * 1997-03-11 1998-09-22 Kansai Paint Co Ltd 室内汚染対策用水性ポリッシュ、水性クリヤ−被覆材、及びこれらを用いた室内汚染低減化方法
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010275196A (ja) * 2009-05-26 2010-12-09 Nippon Soda Co Ltd 透明膜形成液状抗菌剤組成物
WO2011074188A1 (fr) * 2009-12-15 2011-06-23 日本曹達株式会社 Composition liquide transparente antimicrobienne à formation de film
CN102655749A (zh) * 2009-12-15 2012-09-05 日本曹达株式会社 形成透明膜的液状抗菌剂组合物
JPWO2011074188A1 (ja) * 2009-12-15 2013-04-25 日本曹達株式会社 透明膜形成液状抗菌剤組成物
JP5550661B2 (ja) * 2009-12-15 2014-07-16 日本曹達株式会社 透明膜形成液状抗菌剤組成物
CN102655749B (zh) * 2009-12-15 2014-08-27 日本曹达株式会社 形成透明膜的液状抗菌剂组合物
JP2018538298A (ja) * 2015-12-10 2018-12-27 アダマ・マクテシム・リミテッド 高分子電解質層形成ブロックコポリマーならびにその組成物および使用
JP7139246B2 (ja) 2015-12-10 2022-09-20 アダマ・マクテシム・リミテッド 高分子電解質層形成ブロックコポリマーならびにその組成物および使用
JP2020200299A (ja) * 2019-06-10 2020-12-17 三井化学株式会社 易洗浄の衛生材料または生活用品、および微生物の除去方法
JP7421281B2 (ja) 2019-06-10 2024-01-24 三井化学株式会社 易洗浄の衛生材料または生活用品、および微生物の除去方法
WO2024034649A1 (fr) * 2022-08-10 2024-02-15 積水化学工業株式会社 Agent inhibiteur d'infection virale, composition de résine, et produit inhibiteur d'infection virale

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