WO2008004677A1 - Liquid antimicrobial composition capable of forming transparent films - Google Patents

Abstract

The invention aims at providing a liquid antimicrobial composition which is lowly irritant and which can give a transparent film exhibiting high transparency, high persistency of transparency and high persistency of antimicrobial activity when sprayed an object of treatment. The composition is characterized by comprising an organic polymer having a hydrophobic moiety, an antimicrobial component, and water or an alcoholic solvent. The hydrophobic moiety is preferably a non-polar group, more specifically, one or more members selected from the group consisting of alkyl, alkenyl, phenyl, fused polycyclic phenyl and chain polycyclic phenyl.

Description

 Specification

 Transparent film-forming liquid antibacterial agent composition

 Technical field

 [0001] 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.

 Background art

 [0002] The current living environment is highly sealed from the viewpoints of improving the efficiency of air conditioning with an air conditioner and preventing pollen from entering the room. For this reason, various antibacterial agents that prevent the growth of fungi such as fungi and bacteria in the bathroom, around the kitchen, and in window sashes are easy to grow. It has been developed so far.

 [0003] However, places in the bathroom, around the kitchen, window sashes, etc. are easily exposed to moisture, so even if an antibacterial agent is sprayed on those places * even if applied, antibacterial components are eluted by moisture. The antibacterial effect did not last much, and in order to obtain a lasting effect, it was necessary to apply the antibacterial agent frequently and frequently. Thus, attempts have been made to improve the durability of antibacterial agents. For example, 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.

 [0004] In addition, 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.

[0005] On the other hand, in 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. As 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 Water-based anti-algae characterized by containing ~ 10 parts by weight of an anti-algae or fungicide and 0-5 parts by weight of a thickener and adjusting the resin solids concentration to 1-30% by weight (Strong paint) "is described.

 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). In addition, this indicates that “the film thickness after coating is not particularly limited, and can be 0.5 to 20 μm, preferably 1 to 15 μm. Since it is thinner than ~ 200 / ζπι), 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. On the other hand, if it exceeds 30% by weight, the coating thickness becomes too thick, which is preferable because it causes a difference in appearance (外 観) from the unpainted part. ”(Patent Document 2 In addition, in Patent Document 2, it is desirable to make the film thickness as thin as possible. The nature of the components of the latex, much throat coating to reduce the 榭脂 solid concentration not is made form, read it would not be able to form a film thickness 0. 5 m below the coating, for example. For example, when 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. Although it cannot be applied, it is considered that 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.

 [0006] Under such circumstances, there has been a need for a transparent film-forming antibacterial agent composition that is highly transparent when applied to a subject and has a high persistence in antibacterial properties and a high antibacterial effect. Such a transparent film-forming antibacterial composition has not been known so far.

 [0007] Patent Document 1: Japanese Patent Laid-Open No. 10-230976

 Patent Document 2: Japanese Patent Laid-Open No. 2003-292868

 Disclosure of the invention

Problems to be solved by the invention [0008] 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. Hereinafter, “transparent film-forming liquid antibacterial agent composition” is simply referred to as “antibacterial agent composition”.

[0009] 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.

[0010] That is, the present invention relates to the following inventions.

 (1) 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.

 (2) The transparent film-forming liquid antibacterial composition according to (1), wherein the hydrophobic site is a nonpolar group.

 (3) 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 (2), characterized in that

 (Four)

 The transparent film-forming liquid antibacterial composition according to any one of (1) to (3), wherein the organic polymer further has a hydrophilic site.

 (5) The transparent film-forming liquid antibacterial composition according to (4), wherein the hydrophilic part is a polar group.

 (6) Polar group power Carboxyl group, sulfonic acid group, sulfoamide group, amide group, amino group, imino group, hydroxy group, quaternary amino group, oxiamino group, diazonium group, guanidine group, hydrazine group, phosphorus 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.

(7) The transparent film form according to any one of (1) to (6), wherein the organic polymer is a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part Composition liquid antibacterial agent composition.

 (8) The transparent film-forming liquid antibacterial composition according to any one of (1) to (7), wherein the organic polymer is a styrene maleic acid copolymer.

 (9) The transparent film-forming liquid antibacterial composition according to any one of (1) to (8), wherein the formed transparent film has a haze ratio of 5 or less.

 (10) The transparent film-forming liquid antibacterial composition according to any one of (1) to (9), wherein the antibacterial component has a solubility in water of 1Og at 20 ° C of 0.2 g or less.

 (11) The transparent film-forming liquid antibacterial composition according to any one of (1) to (10), wherein the antibacterial component is an antifungal component.

 (12) 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.

 (13) The transparent film-forming liquid antibacterial composition according to any one of (1) to (12), wherein the solubility of the organic polymer in water is 5 to 5000 ppm.

(14) and ethanol in a range of alcoholic solvent power of 20 to 100 weight _^0/0, characterized by comprising the water within a range of 80 to 0% by weight of (1) to (13), Zureka The transparent film-forming liquid antibacterial agent composition described in 1.

 (15) The transparent film formation according to any one of (1) to (14), wherein the weight ratio of the organic polymer to the antibacterial component is in the range of 1:50 to 50: 1. Liquid antibacterial composition.

 (16) The transparent film-forming liquid antibacterial agent according to any one of (1) to (15), wherein the organic polymer is in the range of 0.01 to 10% by weight based on the total amount of the composition Composition.

 (17) The transparent film-forming liquid according to any one of (1) to (16), characterized in that the antibacterial component is in the range of 0.01 to L0% by weight relative to the total amount of the composition. Antibacterial composition.

(18) The transparent film-forming liquid antibacterial agent according to any one of (1) to (17), further comprising a water-soluble metal oxide and Z or amphiphilic metal oxide nanoparticles. composition object.

 (19) The transparent product according to (18), wherein the amphiphilic metal nanoparticles are hydrolysis products of metal chelate compounds having a total of 1 or more hydrolyzable groups and Z or hydroxyl groups. A film-forming liquid antibacterial agent composition.

 (20) Amphiphilic metal oxide nanoparticle force Particle size Inn! The transparent film-forming liquid antibacterial composition according to (18) or (19), wherein the composition is a nanoparticle of ˜30 nm.

 (21) The transparent film-forming liquid antibacterial composition according to any one of (18) to (20), wherein the amphiphilic metal oxide nanoparticles are acid titanium nanoparticles. object.

 (22) 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.

 (23) 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.

Brief Description of Drawings

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.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0012] 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.

 Although the detailed mechanism of the effect of the present invention is unclear, as a result of some interaction between the organic polymer having a hydrophobic site and the antibacterial component, the antibacterial component is stabilized and the antibacterial component Presumably, the precipitation was suppressed.

[0013] 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. 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.

 [0014] 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 thioalcohol group group power of any one selected from preferably one or two or more It can be.

[0015] More specifically, 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.

 From the viewpoint of obtaining a film having higher transparency and transparency persistence and higher durability of the antibacterial effect, 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.

 [0016] 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. Among them, 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. For example, 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.

 In the case of a dicarboxylic acid monomer such as maleic acid or itaconic acid, it is sufficient that it has one carboxyl group and one ester in the state of an organic polymer, but from the viewpoint of obtaining a more excellent effect of the present invention, carboxyl It is preferable to have two groups.

[0017] Monomers having a hydrophobic site include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate. , (Iso) amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- ethenyl hexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl ( (Meth) acrylic acid esters having an alkyl group having 1 to 18 carbon atoms such as styrene; styrene monomers such as styrene, vinyltoluene, 2-methylolstyrene, chlorostyrene, and fragrances such as benzyl (meth) acrylate Examples thereof include ring-containing monomers, among which styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, and chlorostyrene can be preferably exemplified, and styrene can be more preferably exemplified.

[0018] 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.

 [0019] Specific examples of the organic polymer used in the present invention include styrene maleic acid copolymers and derivatives thereof. As the 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. Is used. 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. By reacting the maleic acid copolymer with alcohol, 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.

More specifically, as a polymer used in the present invention, 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.

[0020] The molecular weight of the organic polymer is not particularly limited as long as the effects of the present invention can be obtained. For example, 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.

 Also, the solubility of the organic polymer in water is preferably 5 to 5000 ppm, more preferably 10 to 20 OOppm! /.

 It is also preferable to use a mixture of a plurality of organic polymers having different solubilities. In that case, it is preferable that 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.

 The method for measuring the solubility of the organic polymer is described in the examples described later.

[0021] Examples of the antibacterial component used in the present invention include known antifungal components, antibacterial components, antiyeast components, antiviral components, and the like. For example, 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.

 As used herein, “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. To express. 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. .

[0022] As the antibacterial component, 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. , Jo 1-methyl 1-p-tolylsulfone, 2, 3, 5, 6 tetrachloro 1- (methylsulfol) pyridine, 1— (2— (2, 4 dichlorophenol) —2— (2-probeloxy) Ethyl) 1H-imidazole (imazalyl), among others, thiabendazole, more preferred is thiabendazole and 3 ododo-2-propargyl butyl carbamate. Further, among the antifungal agents, examples of suitable antibiotic agents that can be used in a dispersed manner include 2-methoxycarbonylaminominobenzimidazole, 2-pyridinethiol 1 oxide zinc salt, and the like. be able to. In addition, as 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.

[0023] 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.

 [0024] 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.

In addition, 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. When the coating film is magnified and observed with a microscope, the antibacterial agent crystals are scattered as protrusions in the smooth coating film. However, 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 | crystallization of this antibacterial agent lose | disappeared and the coating film is smooth. On the other hand, 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. When contacted, 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.

[0025] 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.

[0026] 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. There is no particular limitation as long as 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. [0027] 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.

 [0028] 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. As long as it is the following, an optional component may be included in addition to the organic polymer having a hydrophobic site, the antibacterial component, and the alcohol solvent. Examples of such optional components include dispersion stabilizers, surfactants, water repellent components, organometallic compounds, amphiphilic metal oxide nanoparticles, and the like. When a dispersion stabilizer and a surfactant are further included, the antibacterial composition can be dissolved and dispersed more uniformly, which contributes to the sustainability of transparency and the sustainability of the antibacterial effect. In addition, when 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.

[0029] 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 nonanedione , 5-methyl-hexanedione and other multidentate ligand compounds with strong chelating ability to metal atoms; Sulperce 3000, 9000, 17000, 20000 24000 (above, manufactured by General Corporation), Disperbyk-161, 1-162, 1-163,-164 (above, made by Bicchemi), etc., aliphatic amine-based, hydrostearic acid-based or polyesteramine; dimethylpolysiloxane Sun'methyl (polysiloxyalkylene) siloxane copolymer, trimethylsiloxykey acid , Silicone-modified compounds such as carboxy-modified silicone oil, amine-modified silicone and the like (JP-A-9 208438, JP-A 2000-53421, etc.).

 [0030] Examples of the surfactant include surfactants such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Examples of 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. Examples of the cationic surfactant 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 type; Polyethylene glycol fatty acid ester type; Glycerin ester type; POE sorbite fatty acid ester type; Sorbitan fatty acid ester type; Polyoxyethylene sorbitan fatty acid ester type Poleol A— 0638, Pepol B—181, Pepol B—182, Pepol B—184, Pepol B—188, Pepol BEP—0115 (manufactured by Toho Chemical Co., Ltd.), etc. Nonionic surfactants such as oxypropylene alkyl ester type; low bromide polyether can be mentioned.

[0031] 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. In addition to this, Preferable examples include methylpolysiloxane, dimethylsilicone oil, methylhydrogen silicone oil, modified silicone oil, and their emulsions.

 [0032] Examples of the organometallic compound include organometallic compounds containing, for example, titanium, zirconium oxide, aluminum, and silicon.

 Among these, 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.

 [0033] The 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. When 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.

 [0034] 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. As long as it can produce amphiphilic metal oxide nanoparticles, 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. And as a metal compound which has 2 or more of hydrolysable groups and Z or a hydroxyl group in total, the compound represented by Formula (I) can be illustrated preferably.

[0035] R MX (I) [0036] In the above formula (I), 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.

In the above formula (I), 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. Examples of 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;

In the above formula (I), X represents a hydrolyzable group or hydroxyl group bonded to M. Specifically, 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.

[0039] In the above formula (I), a and b each independently represent an integer of 0 to m (m represents a valence of a metal atom) (where a + b = m) ₀ Since the compound represented by the formula (I) is a compound having a total of 2 or more hydrolyzable groups and Z or hydroxyl groups in the molecule, in the formula (I), b is a compound having 2 or more; 1 and R having a hydrolyzable group is 1 or more; B is 0 and R having a hydrolyzable group is 2 or more; Specific examples of the compound represented by the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, etyltrimethoxysilane, etyltriethoxysilane, propyltrimethoxysilane, propinoretriethoxysilane, tetramethoxy. Silane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, 13 (3,4 epoxycyclo

3-Glycidoxypropyltrimethoxysilane, benzyltriethoxysilane, allyltriethoxysilane, vinylmethyldiacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-ataryloxypropyl Silane alkoxides such as trimethoxysilane, 2-chloroethyltriethoxysilane, 4-aminobutyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane; tetramethoxygermanium, tetraethoxygermanium, etc. 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, benzyltrichlorosilane, t-butylphenyldichlorosilane , 3-chloropropyl chlorotrichlorosilane, 8-bromooctyltrichlorosilane, 3-bromopropyltrichlorosilane, (3, 3, 3-trifluor Halogenosilanes such as (ropropyl) dichlorosilane, (3,3,3-trifluoropropyl) trichlorosilane, chloromethyltrichlorosilane, allyltrichlorosilane, 3-ataryloxypropyltrichlorosilane; tetrakis (jetylamino) silane, etc. Other silane compounds such as butylmethylbis (methylethylketoximine) silane; 3, 3, 3-trifluoropropyl methoxydimethoxyhydroxysilane, 3, 3, 3-trifluoropropylmethoxydihydroxysilane, otachinole And hydroxysilanes such as ethoxydihydroxysilane. Among these, 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.

 [0042] 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.

[0043] 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-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, cross-linked aliphatic diamine, 4, 4, 5 Noel) -2, 2, 2-biviridine, O, S, Se, Te coordinated biviridine, alkyliminoviridine, alkylbibilidinylamine, alkyl-substituted tripyridines, di (alkylamino) alkylpyridines, ethylenediaminedipyridine , Other heterocyclic compounds; mercapto alcohols such as 2-mercaptoethanol; Dithiols such as ethanedithiol; mercaptoamines such as 2-mercaptoethylamine; And sulfur-containing compounds such as dithioketones such as 2,4-pentanedithione;

 [0044] As 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 cettonate) aluminum, normal propoxy bis (acetyl cettonate) aluminum, normal butoxy bis (acetyl acetonate) aluminum In particular, diisopropoxybisacetyl cetate titanium can be mentioned as a preferred example.

[0045] 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.

[0046] 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.”). Can be manufactured. In this case, the hydrolysis product may be a complete hydrolysis product or a partial hydrolysis product. Among these hydrolysis products, 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. Of the hydrolysis product As preparation methods, 1) 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. 3) Add the metal chelate compound to the alcohol solution of the antibacterial component, and add water to it. The method described in 3) is particularly preferred, and the preparation is preferably carried out at 0 ° C to room temperature. As the solvent to be used, an alcohol solvent such as ethanol or propanol is preferable.

 [0047] In the production of the hydrolysis product, an acid, a base and Z or a dispersion stabilizer may be added when hydrolyzing with water or after hydrolysis. Examples of 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.

 [0048] The particle size of the amphiphilic metal oxide nanoparticles is 0.8ηπ! ~ 100nm, preferably 1 ηπ! ~ 30nm, more preferably 3ηπ! -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. In addition, the amphiphilic metal oxide nanoparticles are preferable in that they can form nanoparticles with a uniform particle size of amphiphilic acid titanium nanoparticles.

[0049] When the antibacterial agent composition of the present invention contains amphiphilic metal oxide 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. Also, 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.

 [0050] As a method for preventing the generation of bacteria according to the present invention, 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 | coating to the location which grows easily, there will be no restriction | limiting in particular.

 When 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. In the case of 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. Or, 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

 Specifically, the spraying method, the aerosol spraying method, the printing method, the sheet forming method, the dip coating method, the spin coating method, the bar coater method, the Mayer bar method, the brush coating method, and the roller coating method. 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.

[0051] 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.

 [0052] Hereinafter, the present invention will be described more specifically by way of examples. However, the technical scope of the present invention is not limited to these examples.

 Example

[Example A]

 1. Preparation of organic polymers with hydrophobic sites

 (1) Synthesis of styrene maleic anhydride copolymer

In a 500 mL eggplant flask, styrene 16.68 g (0.16 mol), maleic anhydride 17.7 g ( 0.18mol), azobisisobuty-tolyl-tolyl (AIBN) l. 106g (6. 73mol), tetrahydrofuran (hereinafter referred to as "Ding 1 ^" and "ぅ") 20011 ^ are added, mixed and dissolved, and deaerated. After N substitution 60

 2

 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”.

 [0054] (2) Synthesis of styrene maleic anhydride copolymer hydrolyzate

 In a 500 mL eggplant flask, 14.8 g of the previously obtained rosin A was dissolved in 10 mL of acetone, and 150 mL of 1N sodium hydroxide aqueous solution was added dropwise to the solution at room temperature over 1 hour. The mixture was then heated to reflux for 1 hour, allowed to cool, and then 2N hydrochloric acid was added until the pH reached 3. The resulting precipitate was filtered, washed with water and dried to obtain 13.61 g of a styrene maleic acid copolymer. . The yield was 84%. This rosin is hereinafter referred to as “Resin a”.

[0055] 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, and Fig. 2 shows the ¹³ C-NMR chart of rosin a. Figure 3 shows the IR ^ vector of rosin A, and Figure 4 shows the IR ^ vector of rosin a.

[0056] 2. Preparation and film formation of antibacterial agent composition

 The 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. For Comparative Example 1, a commercial product from AP was used.

[0057] [Table 1] Composition sample for strength test and its composition

PAA: Polyacrylic acid

 [0058] 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.

 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.

[0059] 3. Measurement of haze ratio

 The transparency of the film of the film formation sample obtained in 2. above was measured with a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.). As a blank, the transparency of only a vinyl chloride substrate was also measured. The results are shown in Table 2.

[0060] [Table 2] Strength test sample and haze ratio

[0061] According to the results in Table 2, Examples 1 and 2 which are antibacterial agent compositions of the present invention are compared with Comparative Example 1 which contains an organic polymer but does not have a hydrophobic site. Thus, it was shown that the haze ratio is low and the transparency is high.

[0062] 4. 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.

[0063] [Table 3]

 Defense force test results

[0064]: No mold

 : Mycelium only (no problem in practical use)

 +: Mold generation

 + +: Mold equivalent to blank

[0065] It is clear that Examples 1 and 2 have superior antifungal durability compared to Comparative Example 1.

[0066] 5. Examination of optimal ratio of resin a and TBZ

In order to study the optimum ratio of rosin a and TBZ, samples were prepared by the same method as in 2. above, with the ratio of the weight of cocoa a and TBZ varied as shown in Table 4. The TBZ concentration in the antibacterial agent composition used for preparing these film samples was 0.

Each component was used by dissolving in 50 wt% EtOH aqueous solution.

[0067] The haze ratios of these obtained film formation samples were measured in the same manner as in 3. above. The results are shown in Table 4. As a blank, the haze ratio of only the vinyl chloride vinyl substrate was measured and found to be 1.09.

[0068] [Table 4] Resin a-TBZ composition optimization study

[0069] Further, for each of the obtained film formation samples, 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. In addition, 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.

 [Example B]

 1. Preparation of organic polymers with hydrophobic sites

 A commercially available styrene maleic anhydride copolymer was obtained, and the molecular weight was measured by GPC under the same conditions as in Example A. Table 5 shows the molecular weight and copolymerization ratio of each.

 [Table 5] Number average molecule Weight average molecule Main pea copolymerization ratio

 .

 (Styrene

/ Maleic anhydride) 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.

[Table 6]

2. Preparation and film formation of antibacterial agent composition

 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.

[Table 7]

Various composition samples and their compositions

 The remaining composition of each example and comparative example is water.

[0073] 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.

 [0074] 3. Measurement of haze ratio

 Table 8 shows the results of measuring the haze ratio of the above samples using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).

[Table 8] Deposition sample name Haze rate

 Example 2 1. 7 7

 Example 3 1. 8 3

 Example 4 5. 1 3

 Example 5 1. 3 8

 Example 6 2.64

 Example 7 5. 2 2

 Example 8 4. 8 6

 Example 9 3. 4 1

 Example 1 0 2. 24

 Example 1 1 2. 2 7

 Example 1 2 3. 0 6

 Comparative Example 2 1 5. 4 1

 Comparative Example 3 5. 8 0

4. Mold prevention test

 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. In order to perform an accelerated test, 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.

[Table 9]

Water immersion time

 Deposition sample 0 h 2 h 4 h 6 h 8 h 1 0 1 2 1 8 persons hhh Example 2 Earth Soil Earth Soil + + + + Example 3 ― ― ― ― Sat + + + 10 + + Example 4 ― Example + ― + + + + Example 5 ― Doshi Doji Doji Ten Example 6 Doshi ± Dodo

 Example 8 Earth and Earth + + + + + + + Example 9 Earth and Earth Earth and Earth Soil Earth and Earth Earth Example 1 0 Earth and Earth Earth Earth and Earth Soil Earth and Earth Earth Example 1 1 Earth and Earth Earth Soil Earth + 10 + 10 Example 1 2 Satoshi Satoshi Satoshi Satoshi Comparative Example 2 ― ― + + + + + + + + Comparative Example 3 ― Ten + + Ten + + +

One: No mold

Shishi: Mycelium only (no problem in practical use)

+: Mold generation

 + +: Mold occurrence equivalent to blank

 5. Solubility measurement of rosin in water

 The solubility of each resin in water was measured. In the measurement method, pulverized resin lg was weighed into a 140 mL mayonnaise bottle, added to lOOmL ion-exchanged water, and stirred with an lh magnetic stirrer at a water temperature of 25 to 30 ° C. The solution was suction filtered and the filtrate was concentrated with an evaporator. After drying under reduced pressure, the solid content was measured to calculate the solubility in water. The results are shown in Table 10 together with the physical properties when used as an antifungal agent.

[Table 10] Resin used Solubility in water Example Haze of paint film

 / p pm Persistent Resin a 109 Example 2 1. 77 8 h Resin b 1 028 Example 3 1. 83 8 h Resin c 7000 Example 4 5. 13 2 h Resin d 452 Example 5 1. 38 1 2 h Resin e 18 Example 6 2. 64 1 0 h Grease g 139 Example 8 4. 86 4 h

― ― Comparative example 2 1 5. 41 2 h

― ― Comparative example 3 3. 07 <2 h

[0077] 6. Field test

 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)

 Test period: Conducted from May 2006

 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

 Sample No. 2 Comparative Example 2

 Sample No. 3 Example 2

 [Table 11]

 No mold generation

 Slight mold generation

 Force force occurs

[Example C] 1. Preparation and film formation of antibacterial agent composition

<Example 13>

 Fatty resin a: 0.2%, 2, 4, 4, —Trichrome mouth 2, —Noise mouth oxydiphenyl ether: 0.2% was dissolved in a mixture of water: ethanol = 1: 1.

<Example 14>

 Cobalt a: 0.2% and 1,2 benzothiazolone 3: 0.2% were dissolved in a mixture of water: ethanol = 1: 1.

 Here, 2, 4, 4, 1-trichloro-2, 1-hydroxydiphenyl ether and 1,2-benzothiazolone 3 are antibacterial and anti-yeast components.

 The compositions of Examples 13 and 14 were formed by the same method as Example B.

 2. Measurement of haze rate

 The haze ratio was measured by the same method as in Example B. Table 12 shows the measurement results.

[Table 12] Antibacterial · Anti-yeast component-containing transparent film and haze ratio

Industrial applicability

 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.

Claims

The scope of the claims

 [I] A transparent film-forming liquid antibacterial composition comprising an organic polymer having a hydrophobic site, an antibacterial component, and water or an alcohol solvent.

 [2] The transparent film-forming liquid antibacterial composition according to [1], wherein the hydrophobic site is a nonpolar group.

 [3] Nonpolar basic force A group power consisting of an alkyl group, an alkenyl group, a phenyl group, a condensed polycyclic phenyl group, and a chain polycyclic phenyl group. The transparent film-forming liquid antibacterial agent composition according to claim 2.

[4] The transparent film-forming liquid antibacterial composition according to any one of claims 1 to 3, wherein the organic polymer further has a hydrophilic portion.

[5] The transparent film-forming liquid antibacterial composition according to claim 4, wherein the hydrophilic part is a polar group.

 [6] The polar group is a carboxyl group, sulfonic acid group, sulfoamide group, amide group, amino group, imino group, hydroxy group, quaternary amino group, oxiamino group, diazo-um group, guanidine group, hydrazine 6. The group power of a group, a phosphate group, a kainate group, an aluminate group, a nitrile group, and a thioalcohol group, which is selected from one or two or more types. Transparent film-forming liquid antibacterial agent composition.

 7. The transparent film-forming liquid antibacterial agent according to any one of claims 1 to 6, wherein the organic polymer is a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part. Composition.

 8. The organic polymer according to claim 1, wherein the organic polymer is a styrene maleic acid copolymer.

V The transparent film-forming liquid antibacterial agent composition according to any one of the above.

[9] The transparent film-forming liquid antibacterial composition according to any one of [1] to [8], wherein a haze ratio of the formed transparent film is 5 or less.

[10] The transparent film-forming liquid antibacterial composition according to any one of claims 1 to 9, wherein the antibacterial component has a solubility in water of 20 ° C. in water of lOOg of 0.2 g or less.

[II] The transparent film-forming liquid antibacterial composition according to any one of claims 1 to 10, wherein the antibacterial component is an antifungal component.

[12] Antifungal ingredients are thiabendazole, 3-yodo-2-propargylbutylcarbamate, 1,2-benzotriazoline-1-one, jodomethyl-1-p-tolylsulfone, 2, 3, 5, 6 Group power consisting of 4- (methylsulfo) pyridine and 1- (2- (2, 4-dichlorophenyl) — 2— (2-propyloxy) ethyl) — 1H-imidazole (imazalyl) 12. The transparent film-forming liquid antibacterial composition according to claim 11, wherein the composition is at least one kind or two or more kinds.

 [13] The transparent film-forming liquid antibacterial composition according to any one of [1] to [12], wherein the solubility of the organic polymer in water is 5 to 5000 ppm.

[14] and ethanol in a range of alcoholic solvent power of 20 to 100 weight _^0/0, to any one of claims 1 to 13, characterized in that it consists of a 80 to 0 weight _^0/0 water within range of The transparent film formation liquid antibacterial agent composition of description.

 [15] The transparent film-forming liquid antibacterial composition according to any one of [1] to [14], wherein the weight specific force between the organic polymer and the antibacterial component is in the range of 1:50 to 50: 1. .

[16] The transparent film-forming liquid antibacterial composition according to any one of [1] to [15], wherein the organic polymer is in the range of 0.01 to LO weight% with respect to the total amount of the composition. .

[17] The transparent film-forming liquid antibacterial composition according to any one of [1] to [16], wherein the antibacterial component is in the range of 0.01 to LO weight% with respect to the total amount of the composition. object.

[18] The transparent film-forming liquid antibacterial composition according to any one of [1] to [17], further comprising a water-soluble metal oxide and Z or amphiphilic metal oxide nanoparticles.

[19] The method according to claim 18, wherein the amphiphilic metal nanoparticles are hydrolysis products of metal chelate compounds having a total of one or more hydrolyzable groups and Z or hydroxyl groups. A transparent film-forming liquid antibacterial agent composition.

[20] Amphiphilic metal oxide nanoparticle force Particle size Inn! 20. The transparent film-forming liquid antibacterial composition according to claim 18 or 19, wherein the composition is a nanoparticle of ˜30 nm.

21. The transparent film-forming liquid antibacterial composition according to any one of claims 18 to 20, wherein the amphiphilic metal oxide nanoparticles are acid titanium nanoparticles.

[22] The transparent film-forming liquid antibacterial agent composition according to any one of claims 1 to 21, which is a transparent film for windows Forming liquid antibacterial composition, transparent film forming liquid antibacterial composition for kitchen, and transparent film forming liquid antibacterial composition for bathroom.

A spray-type antibacterial agent, wherein the transparent film-forming liquid antibacterial agent composition according to any one of claims 1 to 21 is contained in a container.