WO2011074188A1

WO2011074188A1 - Transparent film-forming, liquid antimicrobial composition

Info

Publication number: WO2011074188A1
Application number: PCT/JP2010/006835
Authority: WO
Inventors: 徹哉佐原; 繁齋藤; 由起子高橋; 英二竹村
Original assignee: 日本曹達株式会社
Priority date: 2009-12-15
Filing date: 2010-11-24
Publication date: 2011-06-23
Also published as: JP5550661B2; CN102655749B; CN102655749A; JPWO2011074188A1

Abstract

Disclosed is a transparent film-forming, liquid antimicrobial composition that has minimal irritating properties, is highly transparent and has highly durable transparency when sprayed on a target, and also has highly durable antimicrobial effects, wherein the transparent film-forming, liquid antimicrobial composition has low solvent odor and is highly safe. The transparent film-forming, liquid antimicrobial composition includes an organic polymer with hydrophobic sites, an acid-soluble antimicrobial constituent with a solubility of no more than 0.2 g per 100 g of 20°C water, an arbitrary alcohol solvent, and water, and is characterized in that the alcohol solvent is less than 20 mass% relative to the entire composition.

Description

Transparent film-forming liquid antibacterial agent composition

The present invention relates to a transparent film-forming liquid antibacterial agent composition that is excellent in transparency and durability of antibacterial effect, and more specifically, since the content of the alcohol component is low, the solvent odor is reduced and the safety is improved. The present invention relates to a transparent film-forming liquid antibacterial composition excellent in transparency and durability of antibacterial effect, and a method for producing the same. The present invention also relates to a transparent film-forming liquid antibacterial composition imparted with light stability by further adjusting the pH and a method for producing the same.
This application claims priority to Japanese Patent Application No. 2009-284428 filed on Dec. 15, 2009 and Japanese Patent Application No. 2010-167495 filed on Jul. 26, 2010. The contents are incorporated here.

The current living environment is highly sealed from the standpoints of improving air-conditioning efficiency with air conditioners and preventing pollen from entering the room. For this reason, fungi such as fungi and bacteria can easily grow in bathrooms, around kitchens, and in windows with sashes, and various antibacterial agents have been used in the past to prevent such fungi from growing. Has been developed.

However, places in the bathroom, around the kitchen, window sashes, etc. are easily exposed to moisture, so even if an antibacterial agent is sprayed or applied to those places, the antibacterial components are eluted by the moisture, and the antibacterial effect is not much. Antibiotics had to be sprayed fairly frequently to achieve lasting and lasting effects. Thus, attempts have been made to improve the durability of antibacterial agents. For example, Patent Document 1 improves the sustainability of the antifungal effect of an antifungal agent by adding a dialkyldimethylammonium salt having a carbon chain length of 10 to 14 as a water repellent film forming component in addition to the antifungal component. Is described. However, the durability of the antibacterial agent was not sufficient.

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 or applied, the solution immediately precipitates. Since it becomes cloudy, it has been more difficult to obtain a continuous antifungal effect. In addition, particularly in indoor applications, precipitation or white turbidity of thiabendazole or the like gives a person who sees an impression of impaired cleanliness, and there is a problem in practical use.

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 and fungi have propagated and biological contamination has progressed, and the biologically contaminated portion can be easily repaired. As a water-based anti-algae (mold) paint, “a water-based anti-algae (mold) paint for building exterior members mainly composed of synthetic resin latex, and 0.01 to 10 weights per 100 parts by weight of resin solids. Water-based anti-algae (mold) paint characterized by containing 1 part by weight of an algae or fungicide and 0 to 5 parts by weight of a thickener and adjusting the resin solids concentration to 1 to 30% by weight Is described.
Patent Document 2 describes that the coating material can be a transparent coating film, but this can be achieved by reducing the resin solid content concentration and reducing the film thickness (see paragraph No. 0031 of Patent Document 2). See description).

The inventors have already proposed a transparent film-forming liquid antibacterial composition having a high transparency and a long lasting antibacterial effect (Patent Document 3). In Examples, 49.6 to A composition containing 99.6% by weight of ethanol is described. Although such a composition exhibits high transparency and long-lasting antibacterial properties, it has a problem that it has a solvent odor (alcohol odor) due to its high solvent content. Moreover, since the content of alcohol, which is a flammable liquid, is high, there is a concern about safety problems.

Under such circumstances, a transparent film-forming antibacterial agent composition having a low solvent odor and a high safety in a transparent film-forming antibacterial agent composition having high transparency and high transparency persistence and high antibacterial effect persistence Things were sought.

Japanese Patent Laid-Open No. 10-230976 JP 2003-292868 A Publication pamphlet of WO2008 / 004677

The present invention is a transparent film-forming liquid antibacterial composition that has low irritation, high transparency when applied to a subject, high transparency, and high antibacterial effect. An object is to provide a transparent antibacterial agent composition with high transparency. Hereinafter, the “transparent film-forming liquid antibacterial agent composition” is simply referred to as “antibacterial agent composition”.

The inventors previously prepared a solution containing an organic polymer having a hydrophobic site, an antibacterial component, and an alcohol solvent, and dispersing the solution in water to obtain a content of the alcohol solvent. Found that an antibacterial composition having a low solvent odor and a high safety can be obtained by such a method, and the inventors have found that an aqueous solution of an antibacterial component and a hydrophobic site It was found that an antibacterial agent composition that is transparent and has a long lasting antibacterial effect can be produced by mixing with an alkaline aqueous solution of an organic polymer having an organic solvent, without using a solvent such as ethanol. It came to complete.

That is, the present invention
(1) An organic polymer having a hydrophobic site, an acid-soluble antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, water, and 0 to less than 20% by mass based on the entire composition Transparent film-forming liquid antibacterial agent composition containing an alcohol solvent of
(2) The transparent film-forming liquid antibacterial composition according to (1), wherein the organic polymer having a hydrophobic site is a styrene-maleic acid copolymer or an acrylic acid polymer,
(3) The transparent film according to (1) or (2) above, wherein the antibacterial component that is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less is thiabendazole or imazalil. A liquid antibacterial composition for liquid formation and (4) a liquid antibacterial composition for forming a transparent film according to any one of the above (1) to (3), wherein the pH is 6.5 or more.

The present invention also provides
(5) (a) An organic polymer having a hydrophobic site, acid-soluble, and an antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less and 0 to less than 20% by mass based on the whole composition Any one of the above (1) to (4), comprising a step of preparing a solution containing an alcohol solvent, and (b) a step of dispersing the solution obtained in step (a) in water. A method for producing a transparent film-forming liquid antibacterial agent composition containing the alcohol solvent according to claim 1,
(6) The method according to (5), wherein the step (b) is a step of adding the solution obtained in the step (a) to water while stirring the water.

Furthermore, the present invention provides
(7) An acid-soluble aqueous solution (A) having a pH of 6 or less containing an antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and an alkali-soluble organic polymer having a hydrophobic site A transparent film-forming liquid antibacterial composition containing no alcoholic solvent according to any one of the above (1) to (4), which is mixed with an aqueous solution (B) containing at least pH 7 containing Method,
(8) The method for producing a transparent film-forming liquid antibacterial composition according to (7) above, wherein the aqueous solution (A) is added to the aqueous solution (B) with stirring.
(9) The method for producing a transparent film-forming liquid antibacterial composition according to (7) or (8) above, wherein the aqueous solution (A) is continuously dropped into the aqueous solution (B).

The antibacterial agent composition of the present invention is a composition comprising an organic polymer having a hydrophobic site, an antibacterial component, water, and optionally an alcohol solvent, and when the alcohol solvent is included, the alcohol It is characterized in that the solvent is less than 20% by mass with respect to the whole composition.

(Organic polymer with hydrophobic sites)
The hydrophobic site of the organic polymer having a hydrophobic site of the present invention (hereinafter sometimes simply referred to as “organic polymer”) is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an s- Alkyl groups such as propyl group, n-butyl group, s-butyl group and t-butyl group; alkenyl groups such as vinyl group, vinylidene group and ethynyl group; phenyl group; condensed polycyclic phenyl groups such as naphthyl group and anthranyl group A phenyl group having a hydrophobic substituent such as a biphenyl group or a terphenyl group; and other nonpolar groups.

The organic polymer of the present invention may not have a hydrophilic part, but from the viewpoint of better transparency, transparency persistence, and antibacterial effect persistence, it further has a hydrophilic part. Preferably it is.
The hydrophilic site is not particularly limited, and examples thereof include a carboxyl group and a metal salt or amine salt thereof; a sulfonic acid group and a metal salt or amine salt thereof; a sulfoamide group; an amide group; an amino group; an imino group; An amino group; an oxyamino group; a diazonium group; a guanidine group; a hydrazine group; a phosphoric acid group; a silicic acid group; an aluminate group; a nitrile group; a thioalcohol group; a phenol group; an alcohol group; an ether 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, Silicic acid group, aluminate group, nitrile group, thioalcohol group, phenol group, alcohol It can be preferably exemplified one kind or two or more species selected from the group consisting of groups and ether groups.

More specifically, examples of the organic polymer used in the present invention include a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part, and a polymer of a monomer having a hydrophilic part and a hydrophobic part. be able to.
From the viewpoint of obtaining a film having higher transparency and transparency persistence and higher persistence of antibacterial effect, a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part is: A random copolymer or an alternating copolymer of both monomers is preferred.

Examples of the monomer having a hydrophobic site include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meta) ) Acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) stearyl (meth) ) (Meth) acrylic acid esters having an alkyl group of 1 to 18 carbon atoms such as acrylate; styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, chlorostyrene, and aromatic rings such as benzyl (meth) acrylate List monomers Bets can be, among others, vinyltoluene, 2-methylstyrene, can be preferably exemplified a styrene-based monomer such as chlorostyrene, it can be mentioned more preferably styrene. In addition, (meth) acrylate has shown the methacrylate or the acrylate.

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-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxy-3-phenoxy Examples thereof include hydroxyl group-containing monomers such as propyl acrylate, 2-hydroxyethyl methacrylate and N-methylolacrylamide; sulfonic acid group-containing monomers such as sodium styrenesulfonate and sulfonated isoprene; amide compound monomers such as acrylamide and methacrylamide. Preferred examples include mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and more preferred examples include dicarboxylic acid monomers such as maleic acid and itaconic acid. It can be.
The monomer having a hydrophilic part used in the present invention may not have a hydrophilic part in the monomer state, and has a hydrophilic part in the state of an organic polymer contained in the antibacterial agent composition. Just do it. For example, the maleic anhydride monomer does not have a hydrophilic site, but in the state of the organic polymer contained in the antibacterial agent composition, the acid anhydride group of maleic anhydride is ring-opened by hydrolysis, resulting in a hydrophilic site. If the carboxyl group which is is produced | generated, it can be said that it is an organic polymer which has a hydrophilic region.
In the case of dicarboxylic acid monomers such as maleic acid and itaconic acid, it is sufficient to have one carboxyl group and one ester in the state of the organic polymer. From the viewpoint of obtaining the more excellent effects of the present invention, the carboxyl group It is preferable to have two.

Examples of the monomer having a hydrophilic part and a hydrophobic part include N-ethyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N- Examples thereof include vinylpyrrolidone, N-vinylcaprolactam, N-isopropenylpyrrolidone, N-isopropenylcaprolactam, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine and the like.

Specific examples of the organic polymer used in the present invention include styrene maleic acid copolymer (SMA) and derivatives thereof.
As the styrene maleic acid copolymer, a compound having a molar ratio of styrene: maleic acid of 5: 1 to 1: 1 is preferable, and a compound of 3: 1 to 2: 1 is more preferable. The styrene maleic acid copolymer derivative means a compound that can be derived from a styrene maleic acid copolymer 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 an alcohol, the acid anhydride group of the maleic anhydride moiety is ring-opened to form a monoester / monocarboxylic acid group copolymer 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 an amine, or a styrene maleic anhydride And a copolymer in which an ester group or a carboxylic acid group formed by ring opening of the acid anhydride group is imidized with an amine.
More specifically, as the organic polymer used in the present invention, a styrene maleic acid copolymer type (TG-750W: manufactured by Kyoeisha Chemical Co., Ltd.) (the acid anhydride group of the maleic anhydride portion of the styrene maleic anhydride polymer is ring-opened) The copolymer is a monoester / monocarboxylic acid group) or an SMA ester resin (manufactured by Sartomer) (an acid anhydride group of the maleic anhydride portion of the styrene maleic anhydride polymer is ring-opened) A copolymer having an ester / monocarboxylic acid group) or an SMA resin: ammonium salt aqueous solution (manufactured by Sartomer) (an acid anhydride group of a maleic anhydride portion of a styrene maleic anhydride polymer is hydrolyzed to form a dicarboxylic acid). Preferred examples thereof include copolymers having acid groups.

The molecular weight of the organic polymer is not particularly limited as long as the effect of the present invention is obtained. For example, the number average molecular weight is preferably in the range of 1,000 to 200,000, and is preferably in the range of 3,000 to 100,000. It is more preferable that
Further, the solubility of the organic polymer in water at 20 ° C. is preferably 5000 ppm or less, and more preferably 2000 ppm or less.
As the organic polymer, a plurality of organic polymers can be mixed and used.

(Antimicrobial component)
The antibacterial component used in the present invention is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less.
There is no limitation as long as the conditions are satisfied, and for example, known antifungal components, antibacterial components, antiyeast components, antiviral components and the like (hereinafter, sometimes simply referred to as antibacterial components) can be used.
Specifically, as antibacterial components, thiabendazole (TBZ), 1- (2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H-imidazole (imazalyl), 2-methoxycarbonylamino Imidazole compounds such as benzimidazole (carbendazine), thiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole (TCMTB), (RS) -1-p-chlorophenyl-4,4-dimethyl- Examples thereof include triazole compounds such as 3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (tebuconazole).
Of these, thiabendazole and imazalyl are preferable, and thiabendazole is particularly preferable.

(Water, alcohol solvent)
The antimicrobial composition of the present invention contains water and optionally an alcohol solvent.
As water, any of ultrapure water, distilled water, ion-exchanged water, tap water, city water, industrial water, and the like may be used and may be appropriately selected.
Examples of the alcohol solvent include C1-C10 alcohols such as methanol, ethanol, isopropyl alcohol, etc., but it is preferable to use ethanol. One kind of alcohol may be used alone, or two or more kinds of alcohols may be contained.

(Composition)
In the antibacterial agent composition of the present invention, water or a mixed solvent of water and an alcohol solvent is a solvent component, and an organic polymer having a hydrophobic site and an antibacterial component are dissolved and / or dispersed in the solvent component. However, among the solvent components, the alcohol solvent is less than 20% by mass with respect to the composition. Since the alcohol solvent does not necessarily have to be contained, there is no lower limit to this value.

The antibacterial agent composition of the present invention has a haze ratio of 5.0 or less, preferably 3.0 or less, after 24 hours from the application of a 20 to 300 nm thick film formed by spray coating on a vinyl chloride substrate. Preferably it is 2.0 or less.
The haze rate was determined by drying a coating film sprayed on a transparent vinyl chloride plate having a thickness of 0.5 mm (manufactured by Acrysanday, transparent hard vinyl chloride plate, haze ratio: 1.0 to 1.3) at room temperature for 24 hours. The sample thus obtained can be measured with a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd.

The content of the organic polymer in the antibacterial agent composition of the present invention is not particularly limited as long as desired transparency and performance can be obtained, but is preferably 1 to 10 with respect to the total amount of the antibacterial agent composition. % By mass, more preferably 1.2 to 5% by mass.

The content ratio of the antibacterial component in the antibacterial agent composition of the present invention is not particularly limited as long as the desired antibacterial performance is obtained, but is preferably 0.01 to 5% by mass relative to the total amount of the antibacterial agent composition. Preferably, the content is 0.05 to 1% by mass.

The blending ratio (mass ratio) of the organic polymer and the antibacterial component in the antibacterial agent composition of the present invention is not particularly limited as long as the desired antibacterial performance can be obtained. -50, more preferably 10-20.

Moreover, the antibacterial agent composition of this invention can improve the photostability of a chemical | medical solution and a coating film by adjusting pH, and can prevent yellowing. The pH at this time is 6.5 or more, preferably 6.5 to 9, and more preferably 7 to 9.
The pH can be adjusted by adding an arbitrary pH adjusting agent. As the alkaline substance, an aqueous solution such as sodium hydroxide, potassium hydroxide, triethanolamine, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate and the like, which are used for usual pH adjusters, can be used.

(Optional component)
The antibacterial agent composition of the present invention may contain an optional component in addition to the organic polymer having a hydrophobic site, the antibacterial component, water and an alcohol solvent. Examples of such optional components include surfactants, water-soluble polymer compounds, leveling agents, antifoaming agents, and water repellent components. The surfactant can dissolve and disperse the antibacterial agent composition more uniformly, contributing to the persistence of transparency and the sustainability of the antibacterial effect. The water-soluble polymer compound can stably spread and hold an antibacterial component or the like on the ceiling and wall surface of the bathroom inner surface over a predetermined period. The leveling agent can make the surface tension of the coating film uniform, prevent floating and repellency, and improve the wettability to an object. Further, the antifoaming agent can prevent foam residue on the surface of the coating film.

Examples of surfactants include surfactants such as nonionic surfactants. Nonionic surfactants include alkylol amide type; pegnol L-4, pegnol TH-8, pegnol L-9A, pegnol L-12S, pegnol L-20S, pegnol T-6, pegnol TE-10A, pegnol ST-7, pegnol ST-9, pegnol ST-12, pegnol O-6A, pegnol O-107, pegnol O-16A, pegnol O-20, pegnol O-24, pegnol C-18, pegnol S-4D, pegnol Polyoxyethylene alkyl ether types such as HC-10 (manufactured by Toho Chemical Industry Co., Ltd.), Emulgen 705, Emulgen 707, Emulgen 709 (manufactured by Kao Corporation); polyethylene glycol fatty acid ester type; glycerin ester type; P.O.E Sorbit fatty acid ester type; Sol Polyoxyethylene sorbitan fatty acid ester type; Pepol A-0638, Pepol B-181, Pepol B-182, Pepol B-184, Pepol B-188, Pepol BEP-0115 (manufactured by Toho Chemical Co., Ltd.) Polyoxyethylene polyoxypropylene alkyl ether type such as: NIKKOL HCO-40, NIKKOL HCO-60, NIKKOL HCO-100 (manufactured by Nikko Chemicals), etc .; 1-M, NIKKOL Decaglyn 1-50SV, NIKKOL Hexaglyn 1-L, NIKKOL Hexaglyn 1-M, NIKKOL Hexaglyn Polyglycerin fatty acid ester type such as 1-SV (Nikko Chemicals); low bromide polyether, New Calgen CP120, CP-15-150, CP-15-200, D-945, D-935 (Takemoto Yushi Co., Ltd.) Company-made).

The water-soluble polymer compound may be a natural water-soluble polymer, a synthetic water-soluble polymer, or a mixture thereof. Examples of the synthetic water-soluble polymer include polyacrylamide, polyacrylic acid, polymethacrylic acid, and polyitaconic acid. , Polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl methyl ether, or a water-soluble polymer obtained by copolymerizing maleic acid, fumaric acid, crotonic acid, anicotic acid and the like with other monomers. Examples of the polymer include various starches, proteins, cellulose, hydroxypropylcellulose, carboxymethylcellulose and the like.

As the leveling agent, New Calgen D-1420, New Calgen A-28-B (all made by Takemoto Yushi Co., Ltd.), as the antifoaming agent, New Calgen 1028PB, Pionin K-17 (all made by Takemoto Yushi Co., Ltd.), etc. These known agents can be used.

Further, as the water repellent component, MegaFuck F-475 (Dainippon Ink Co., Ltd.), MegaFuck F-480SF (Dainippon Ink Co., Ltd.), MegaFuck F-470 (Dainippon Ink Co., Ltd.), Fluorosurfactants such as MegaFuck F-482 (Dainippon Ink Co., Ltd.), Dickguard F-90N (Dainippon Ink Co., Ltd.), Dickguard TE-5A (Dainippon Ink Co., Ltd.), Fluorine fiber processing agents such as Dickguard F-445 (Dainippon Ink Co., Ltd.) can be preferably exemplified. In addition, dimethylpolysiloxane, dimethyl silicone oil, methyl hydrogen silicone oil, modified silicone oil, or emulsions thereof can be preferably exemplified.

(Production method)
The antibacterial agent composition of the present invention differs in production method between the case of containing an alcohol solvent and the case of not containing an alcohol solvent. Hereinafter, each method will be described in detail.

(1) When containing an alcohol solvent The production method when the antibacterial agent composition of the present invention contains an alcohol solvent is as follows: (a) an organic polymer having a hydrophobic site, acid-soluble, and 20 ° C A step of preparing an antibacterial component having a solubility in 100 g of water of 0.2 g or less and a solution containing an alcohol solvent of less than 20% by mass based on the whole composition; and (b) obtained in the step (a). A step of dispersing the dissolved solution in water. As the organic polymer having a hydrophobic site, an acid-soluble antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and the alcohol solvent, those described above can be used.
The solution of step (a) may further contain components such as water, a surfactant, a leveling agent, and an antifoaming agent as necessary. When preparing a solution containing water in the step (a), 50% or less, preferably 5 to 30%, of water contained in the final antibacterial agent composition can be added.
Well-known conditions and methods can be used for preparation of the solution of a process (a). For example, a stirring and mixing device can be used, and specifically, a magnetic stirrer, a mixer, a homogenizer, a stirring blade stirrer, or the like can be used.

The step (b) is a step of dispersing the solution obtained in the step (a) in water. If necessary, a part or all of a surfactant, a leveling agent, an antifoaming agent, etc. may be added to the step ( The solution obtained in a) may be dispersed simultaneously with the solution obtained in step a), or the solution obtained in step (a) may be dispersed in a solution obtained by previously mixing a part or all of water and the above agent.
Known conditions and methods can be used for dispersion. Specifically, the same ones as those mentioned in step (a) can be used, and the solution obtained in step (a) while stirring water. A method in which is added to water and dispersed is preferred.

(2) When not containing alcohol solvent The production method when the antibacterial agent composition of the present invention does not contain an alcohol solvent is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less. An aqueous solution (A) having a pH of 6 or less containing an antibacterial component is mixed with an aqueous solution (B) having a pH of 7 or more containing an organic polymer that is alkali-soluble and has a hydrophobic site.

(2-1) Preparation of aqueous solution (A) The above antibacterial component and acidic compound are mixed to prepare an aqueous solution (A) having a pH of 6 or less, preferably 4 or less, in which the antibacterial component is dissolved.
The content of the antibacterial component in the obtained aqueous solution (A) is not particularly limited as long as the antibacterial component is dissolved, but is usually 0.01 to less than 20% by mass, preferably 0.01 to 5% by mass, Preferably, the content is 0.01 to 1% by mass.
Mixing can be performed by a known method, and is usually heated and mixed, but heating is not necessary when the acid concentration is high.
Acids that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid, organic acids such as maleic acid, oxalic acid, citric acid and malic acid, acidic ion exchange resins, and antibacterial components Depending on the type, the type and concentration of the acid to be used can be appropriately selected.

(2-2) Preparation of aqueous solution (B) The above organic polymer and alkaline aqueous solution are mixed to prepare an aqueous solution (B) having a pH of 7 or more in which the organic polymer is dissolved.
The content of the organic polymer in the obtained aqueous solution (B) is not particularly limited as long as the organic polymer is dissolved, but is usually 1 to 50% by mass, preferably 5 to 20% by mass.
Mixing can be performed by a known method, and is usually heated and mixed. However, heating is not necessary when the alkali concentration is high.
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; ammonia, triethanolamine, sodium carbonate, carbonate Examples thereof include potassium, sodium phosphate, sodium citrate, basic ion exchange resin, and the like, and the type and concentration of the alkali to be used may be appropriately selected depending on the type of the organic polymer.

(2-3) Preparation of antibacterial agent composition The antibacterial agent composition produced by this method can be produced by mixing the aqueous solution (A) and the aqueous solution (B). Moreover, in order to adjust pH at the time of mixing, you may add an acid or an alkali as needed. Furthermore, you may add various solvents and additives as needed.
The pH of the antibacterial agent composition of the present invention is not particularly limited as long as the antibacterial component and the organic polymer are dissolved and transparent.
The mixing method is usually carried out by adding the aqueous solution (A) to the aqueous solution (B) and stirring. In particular, the aqueous solution (A) is dropped continuously or discontinuously into the aqueous solution (B). It is preferable to stir with stirring.
Here, “continuous dripping” means dripping without interruption, and “non-continuous dripping” means dripping at intervals.
The temperature at the time of mixing is not particularly limited, but is preferably room temperature or higher in order to prevent precipitation of components.
As a stirring means, for example, a stirrer, a magnetic stirrer, a mixer, a homogenizer, a homodisper or the like may be stirred in the tank, and a method of mixing in a pipe with a line mixer may be used.
Since acid and alkali are usually used as an aqueous solution, no special treatment is required. However, when an acidic ion exchange resin or a basic ion exchange resin is used, the ion exchange resin can be removed by filtration or the like.
The salt produced when the aqueous solution (A) and the aqueous solution (B) are mixed may be removed by dialysis, ion exchange resin, or the like, if necessary.

(how to use)
The antibacterial agent composition of the present invention can be used to prevent the occurrence of fungi by using the antibacterial agent composition of the present invention as a rubber packing for windows; ceilings in the bathroom, wall surfaces, drain outlets, tile joints; There is no particular limitation as long as it is a method of applying to a place where mold or the like is likely to grow.
When the antibacterial agent composition of the present invention is a composition containing an antifungal agent as an active ingredient, the rubber packing of the window; the ceiling of the bathroom, the wall surface, the vicinity of the drain, the joint of the tile; It is used for the purpose of preventing the occurrence of mold by applying to easy-to-use areas. In the case of a composition containing an antibacterial or 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 generating bad odors. Used for the purpose.
Specific examples of the application method include a spray spraying method, an aerosol spraying method, a bar coater method, a Mayer bar method, a brush coating method, a roller coating method, and the like, but the spray spraying method is preferable. The coating amount of the antibacterial agent composition and the thickness of the film formed by the antibacterial agent composition are not particularly limited, but preferably the film thickness is in the range of 5 to 500 nm, more preferably in the range of 20 to 300 nm. Can do.

The spray-type antibacterial agent 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 the container can spray the contents. When a large area is applied, the load on the operator increases due to the increase in the number of sprays. Therefore, the sponge or a spatula that forms a fine and uniform gap between the application surface and the sponge is soaked in the drug. It can also be used.
When spreading with a sponge or the like, it is preferably performed before the volatile component in the drug volatilizes. Even if the volatile components are volatilized and spread, a non-uniform film is formed, and a site where the antibacterial effect is reduced tends to occur.
Since the antibacterial agent composition of the present invention contains 0 to less than 20% by mass of an alcohol solvent with respect to the entire composition, the volatile component volatilizes at an appropriate rate, and therefore it is easy to spread. However, when the alcohol solvent is contained in an amount of 20% by mass or more, the volatilization is fast and unsuitable for spreading.

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.

(1) When containing an alcohol solvent [antibacterial agent composition]
Antibacterial compositions of Examples 1 and 2 having the compositions shown in Table 1 were prepared.
Each antibacterial composition was prepared by dissolving 30 parts by mass of water in 100 parts by mass of ethanol and the resin, antibacterial component, and surfactant described in Table 1. This was produced by slowly dropping it into 30 parts by mass less than a predetermined amount while stirring with a magnetic stirrer at room temperature.

In Table 1, resin a is a styrene maleic acid copolymer resin {number average molecular weight 7200, copolymerization ratio 2.2: 1 (styrene: maleic acid, molar ratio)}, and resin b is a styrene maleic acid resin {number average. The molecular weight is 60,100, and the copolymerization ratio is 1.0: 1 (styrene: maleic acid, molar ratio)}.
Surfactant A is New Calgen CP-120 (manufactured by Takemoto Yushi Co., Ltd.), and Surfactant B is New Calgen CP-15-200 (manufactured by Takemoto Yushi Co., Ltd.).

[Test Example 1] Storage stability Stability immediately after preparation of the antibacterial agent composition was evaluated. The solution state was visually observed 1 hour after stirring was stopped when the antibacterial agent composition was prepared. Evaluation was made according to the following criteria.
○: Clear liquid, △: Slightly turbid, ×: Cloudy and sedimentation component generation In the stability evaluation immediately after preparation of the antibacterial agent composition, 5 parts by mass were measured in a vial with no cloudiness or sedimentation component generation A storage stability test was performed. The test conditions and evaluation criteria are as follows.
Test conditions: 0 ° C. (1 month), room temperature (1 month), 40 ° C. (1 month)
Evaluation criteria: ○: Clear liquid, △: Slightly turbid, ×: Cloudy and sedimentation component generation

[Test Example 2] Evaluation of fungicidal performance during spray application In the stability evaluation immediately after preparation of the antibacterial agent composition, those that were not cloudy and did not generate sediment components were spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m ² . Each coating film was cut into 4 cm × 7.5 cm and immersed in ion exchange water (50 mL) for a predetermined time to evaluate the anti-mold performance after drying. The antifungal performance was evaluated by placing a 4cm x 4cm test piece on a potato dextrose agar medium, applying a mixture of black mold mold spores and liquid medium, and culturing at 25 ° C for 1 week. Judged by. Those with no mold were marked as-(minus) and those with mold were marked as + (plus).

[Test Example 3] Transparency Evaluation In the stability evaluation immediately after the preparation of the antibacterial agent composition, those that were not cloudy and did not generate sediment components were spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m ² . The transparency of each coating film was visually evaluated. The transparent one was marked with ◯, and the whitened one was marked with ×.

[Test Example 4] Evaluation of ethanol odor For those having no cloudiness and no sediment component in the stability evaluation immediately after the preparation of the antibacterial agent composition, it was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m ² . The ethanol odor during the spray application operation was evaluated. During work, ◎ indicates that there is little odor, ◯ indicates that there is a slight odor but does not bother, and × indicates that the odor is strong.

[Test Example 5] Evaluation of ethanol ignitability The ignitability when each antibacterial agent composition was sprayed toward a flame was evaluated. A spray bottle that injects about 1 g per push was used. One push was performed from a distance of 20 cm to a gas stove that was lit, and the change in flame was visually observed and evaluated according to the following criteria. The one that did not ignite was marked with ○, and the one with a large flame was marked with ×.

[Test Example 6] Evaluation of ignitability to chemical solution 5 mL of the antibacterial agent composition was placed in a glass petri dish, and an ignition test was conducted by bringing the flame closer. Those that did not ignite were marked with ○, those that ignited and burned were marked with ×.

The results of Test Examples 1 to 6 are summarized in Table 2.

(2) When no alcohol solvent is contained [Examples 3 to 10]
1) Preparation of thiabendazole (TBZ) aqueous solution 99.6 parts by mass of 0.025N hydrochloric acid was added to a beaker, and 0.4 part by mass of TBZ was added to prepare a 0.4 mass% TBZ aqueous solution (pH 2.5). Placed at 30 ° C. for 30 minutes.
2) Preparation of Styrene Maleic Acid Copolymer Resin (SMA) Na Salt Aqueous Solution In a 500 mL eggplant flask, 20 parts by mass of three commercially available styrene maleic anhydride resins were dissolved in 200 mL of acetone. Then, 400 mL of 1N aqueous sodium hydroxide solution was added dropwise over 1 hour. The mixture was then heated to reflux for 1 hour, and after cooling, 2N hydrochloric acid was added until the pH reached 3, and the resulting precipitate was filtered off, washed with water and dried, so that the three types of styrene maleic acid co-polymers shown in Table 3 were used. In each case, 19 parts by mass were obtained.
It was confirmed by ¹³ C-NMR, IR and the like that the product had no unreacted maleic anhydride moiety.

30 mL of 1N sodium hydroxide aqueous solution and 60 mL of water are put into a beaker, and 10 g of SMA shown in Table 3 above is added to prepare three types of 10 mass% SMA-Na salt aqueous solutions (pH 8), which are placed at 60 ° C. for 1 hour. It was.

3) Preparation of antibacterial agent composition Into the flask, the SMA-Na salt aqueous solution prepared in 2) above (added so as to have the resin amount in Table 4) and water (SMA-Na salt aqueous solution and TBZ aqueous solution) were subtracted. While stirring with a magnetic stirrer in the amount of water, the aqueous TBZ solution prepared in 1) above (added so as to have the amount of TBZ in Table 4) was dropped to prepare the antibacterial agent composition shown in Table 4. If necessary, pH adjustment was performed using 1N aqueous sodium hydroxide solution and 1N hydrochloric acid. In Example 6, a predetermined amount of ethanol was added after these operations.

[Example 11]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that a 0.1% by mass aqueous solution of imazalil was prepared using 0.1N hydrochloric acid.
[Example 12]
An antibacterial composition was prepared in the same manner as in Example 9, except that Decagulin 1-L (surfactant manufactured by Nikko Chemicals) was added.
[Example 13]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that a 0.1% by mass aqueous solution of carbendazine was prepared using 0.1N hydrochloric acid.
[Example 14]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that 1N hydrochloric acid was used to prepare a 0.06 mass% aqueous solution of tebuconazole.
[Comparative Example 6]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that no resin was added.
[Comparative Example 7]
An antibacterial composition was prepared in the same manner as in Example 9 except that polyacrylic acid (resin D) in which the resin did not have a hydrophobic site was used.
[Comparative Example 8]
Resin and TBZ were directly added to water so as to have the blending amounts shown in Table 4, respectively, and mixed and stirred to obtain an antibacterial agent composition.
TBZ did not dissolve and a sediment component was generated.

[Test Example 7] Evaluation of fungicidal performance during spraying The antibacterial agent composition was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 30 g / m ² . Each coating film was cut into 4 cm × 7.5 cm and immersed in ion exchange water (50 mL) for a predetermined time to evaluate the anti-mold performance after drying. The antifungal performance was evaluated by placing a 4cm x 4cm test piece on a potato dextrose agar medium, applying a mixture of black mold mold spores and liquid medium, and culturing at 25 ° C for 1 week. Judged by. The samples immersed for each immersion time were observed for the presence or absence of mold, and those with no spores were assumed to maintain mold prevention performance. The water resistance was evaluated based on the immersion time during which the antifungal performance was maintained.

[Test Example 8] Transparency evaluation The antibacterial agent composition was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 30 g / m ² . The transparency of each coating film was visually evaluated. The transparent one was marked with ◯, and the whitened one was marked with ×.

[Test Example 9] Light stability evaluation 2 g of the antibacterial agent composition was placed in a plastic petri dish having a diameter of 9 cm and allowed to stand at room temperature to dry. The lid was opened under direct sunlight and left for 6 hours. The petri dish after being allowed to stand was observed, where を was not colored, ◯ was slightly colored, and x was yellowed.

[Test Example 10] Storage stability evaluation The antibacterial agent composition was placed in a sample bottle, and the storage stability at a predetermined temperature was judged visually. The case where no change was observed and the case where the precipitate was observed was rated as わずか, the case where a slight precipitate was observed was marked as ◯, and the case where the sediment component was generated was marked as x.

[Test Example 11] Evaluation of easiness of spreading spread A 45 cm × 30 cm vinyl chloride substrate was blown using a residential detergent spray container (manufactured by Kao Corp.), and a commercially available sponge (softened, water) Spread easily.
The slipperiness of the sponge was evaluated. The case where there was no catch was rated as ◎, the case where the catch was once, Δ, and the case where the catch was 2 times or more as x.
The evaluation results of Test Examples 7 to 11 are shown in Table 5.

[Comparative Examples 9 to 14]
A composition having the composition shown in Table 6 was prepared. These compositions are 1N KOHaq. A 50 mass% ethanol aqueous solution or ion exchange water and ethanol were added to the mixture, and SMA and TBZ were further added, mixed, and stirred for 30 minutes or more.
The state of the solution immediately after preparation of the antibacterial agent composition was visually observed, and the transparency was evaluated according to the following criteria.
○: Clear liquid Δ: There is a very small amount of sediment ×: There is a sediment In Table 6, “SMA3000” is the styrene-maleic acid copolymer resin of resin C in Table 3 above.

The antibacterial agent composition of the present invention has high transparency and long-lasting antibacterial effect when applied to an object, and has a low solvent content, so that the solvent odor is low during production and use, and the safety is high.
In addition, the production method of the present invention can provide a transparent film even when an antibacterial component is contained at a high concentration as compared with the conventional production method, so that the antibacterial performance can be enhanced. Furthermore, yellowing of the antibacterial agent composition can be prevented by adjusting the pH of the antibacterial agent composition, and the workability is good even when spreading using the present invention.

Claims

An organic polymer having a hydrophobic site, an acid-soluble antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, water, and an alcohol system having a content of 0 to less than 20% by mass with respect to the entire composition A transparent film-forming liquid antibacterial composition containing a solvent.
The transparent film-forming liquid antibacterial composition according to claim 1, wherein the organic polymer having a hydrophobic site is a styrene-maleic acid copolymer or an acrylic acid polymer.
3. The transparent film-forming liquid antibacterial composition according to claim 1 or 2, wherein the antibacterial component which is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less is thiabendazole or imazalil. .
The transparent film-forming liquid antibacterial composition according to any one of claims 1 to 3, wherein the pH is 6.5 or more.
(A) an organic polymer having a hydrophobic site, an acid-soluble antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and an alcohol solvent of 0 to less than 20% by mass based on the entire composition The alcohol system according to any one of claims 1 to 4, further comprising: a step of producing a solution containing a solution; and (b) a step of dispersing the solution obtained in step (a) in water. A method for producing a transparent film-forming liquid antibacterial composition containing a solvent.
The production method according to claim 5, wherein the step (b) is a step of adding the solution obtained in the step (a) to the water while stirring the water.
An aqueous solution (A) having a pH of 6 or less containing an antibacterial component which is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and an alkali-soluble organic polymer having a hydrophobic site The method for producing a transparent film-forming liquid antibacterial composition containing no alcohol solvent according to any one of claims 1 to 4, wherein the aqueous solution (B) having a pH of 7 or more is mixed.
The method for producing a transparent film-forming liquid antibacterial composition according to claim 7, wherein the aqueous solution (A) is added to the aqueous solution (B) while stirring.
The method for producing a transparent film-forming liquid antibacterial composition according to claim 7 or 8, wherein the aqueous solution (A) is continuously dropped into the aqueous solution (B).