JP2015078133A - Antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antimicrobial composition having improved antibacterial effect and improved safety.SOLUTION: The antibacterial composition contains calcium oxide and a polyalkylene biguanide compound having a structure represented by the chemical formula (1) and/or a salt thereof. (1), where Rrepresents an alkylene group having 2 to 8 carbon atoms and n represents an integer of 2 to 18.

Description

  The present invention relates to an antimicrobial composition.

  Common antibacterial agents such as benzalkonium chloride are limited to bacterial species that can sufficiently exhibit antibacterial action, and are ineffective against highly resistant bacteria (for example, heat-resistant spore bacteria). On the other hand, according to the antibacterial agent using the biguanide compound, it is known that the antibacterial effect can be exhibited even with a strong resistant bacterium and the antibacterial effect can be exhibited with a relatively small amount of use (Patent Document 1). .

  However, an antibacterial agent having further improved antibacterial action and further improved safety is desired.

JP 2012-171926 A

  The present invention has been made to solve the above conventional problems, and an object of the present invention is to provide an antibacterial composition having further improved antibacterial action and further improved safety.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by using calcium oxide and a biguanide compound in combination, and have completed the present invention.

［化学式（１）中、Ｒ^ａは炭素数２〜８のアルキレン基を表し、ｎは２〜１８の整数を表す。］
好ましい実施形態においては、上記酸化カルシウムは、平均粒径１０μｍ以下の粒子の形態である。
好ましい実施形態においては、上記酸化カルシウムは、炭酸カルシウムを含む生物材料を焼成して得られる。
好ましい実施形態においては、上記抗菌性組成物は、化学式（２）で表される構造を有する第４級アンモニウム塩をさらに含む。

［化学式（２）中、Ｒ^１およびＲ^２はそれぞれ独立して、炭素数８〜１８のアルキル基を表し、Ｒ^３およびＲ^４はそれぞれ独立して、炭素数１〜４のアルキル基を表し、Ａ⁻は無機または有機の陰イオンを表す。］ The antibacterial composition of the present invention is
With calcium oxide;
And a polyalkylene biguanide compound having a structure represented by the chemical formula (1) and / or a salt thereof.

In Chemical Formula (1), ^{R a} represents an alkylene group having 2 to 8 carbon atoms, n is an integer of 2 to 18. ]
In a preferred embodiment, the calcium oxide is in the form of particles having an average particle size of 10 μm or less.
In a preferred embodiment, the calcium oxide is obtained by baking a biological material containing calcium carbonate.
In a preferred embodiment, the antibacterial composition further includes a quaternary ammonium salt having a structure represented by the chemical formula (2).

[In the chemical formula (2), R ¹ and R ² each independently represent an alkyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. , A ⁻ represents an inorganic or organic anion. ]

  In the antibacterial composition of the present invention, calcium oxide and the biguanide compound synergistically exhibit a high antibacterial action. As a result, the amount of biguanide compound used can be reduced as compared with the prior art. Furthermore, calcium oxide is an extremely safe substance. Therefore, according to the present invention, an antibacterial composition with further improved antibacterial action and further improved safety can be provided.

  Hereinafter, although preferable embodiment of this invention is described, this invention is not limited to these embodiment.

[A. Antibacterial composition]
The antibacterial composition of the present invention contains calcium oxide; and a polyalkylene biguanide compound having a structure represented by the above chemical formula (1) and / or a salt thereof.

  As used herein, “antibacterial composition” means a composition that removes or reduces the infectious and / or proliferative ability of bacteria. Therefore, the antibacterial composition does not necessarily have a sterilizing action and / or bactericidal action, and any antibacterial composition may be used as long as it reduces the ability of bacteria to infect and / or grow in the host organism. .

  Arbitrary appropriate forms can be employ | adopted as a form of the said antimicrobial composition. Examples of the form include liquid, paste, gel, milk, and solid. When the form is liquid, the antibacterial composition can act on a wide range of disinfecting objects in a short time. The antimicrobial composition can include a carrier. Examples of the carrier include a liquid carrier, a gel carrier, an emulsion, and a solid carrier. Any appropriate liquid carrier can be adopted as the liquid carrier. Examples of the liquid carrier include water, organic solvents, and mixtures thereof. Examples of the organic solvent include lower alcohols and polyhydric alcohols. Examples of the lower alcohol include ethanol, isopropanol, and butanol. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, and butylene glycol. When water or a mixture of water and an organic solvent is used as the liquid carrier, handleability (for example, corrosiveness to an object to be disinfected) and economy are improved.

  The antibacterial composition preferably has a pH of 10 to 13, more preferably 10.5 to 12.5, and particularly preferably 11 to 12. The pH of the antibacterial composition can be adjusted using, for example, a buffer and / or a pH adjusting agent. Any appropriate buffer can be used as the buffer. Examples of the buffer include citrate-phosphate buffer, phosphate buffer, tris (hydroxymethyl) aminomethane-hydrochloric acid buffer, and glycine-sodium hydroxide buffer. Any appropriate pH adjusting agent can be used as the pH adjusting agent. Examples of the pH adjuster include lactic acid, citric acid, gluconic acid, succinic acid, potassium carbonate, sodium hydrogen carbonate, and sodium hydroxide.

  The antibacterial composition contains calcium oxide in an amount of usually 0.0001% to 1% by weight, preferably 0.001% to 0.5% by weight, more preferably 0.01% to 0.25% by weight. contains.

  The antibacterial composition contains the polyalkylene biguanide compound and / or salt thereof in an amount of usually 0.0001% to 2.5% by weight, preferably 0.001% to 1.2% by weight, more preferably 0%. 0.01% by weight to 0.5% by weight.

  The antibacterial composition may further include a quaternary ammonium salt having a structure represented by the chemical formula (2). When the antibacterial composition further contains the quaternary ammonium salt, the antibacterial effect is further improved.

  The antibacterial composition contains the quaternary ammonium salt usually in an amount of 0% to 0.5% by weight, preferably 0.001% to 0.4% by weight, more preferably 0.01% to 0%. .Contains 25% by weight.

  The antibacterial composition preferably contains calcium oxide and the polyalkylene biguanide compound and / or salt thereof in a weight ratio (the former: the latter) of 9: 1 to 1: 9, and 7: 3 It is more preferable to contain it in a ratio of ˜3: 7. When the antibacterial composition contains calcium oxide and the polyalkylene biguanide compound and / or salt thereof in such a weight ratio, the antibacterial effect is further improved.

  The antibacterial composition preferably contains calcium oxide and the quaternary ammonium salt in a weight ratio (the former: the latter) of 1: 0 to 1: 1, and 30: 1 to 4: 1. It is more preferable to contain in the ratio. When the antibacterial composition contains calcium oxide and the quaternary ammonium salt in such a weight ratio, the antibacterial effect is further improved.

  The antibacterial composition preferably contains the polyalkylene biguanide compound and / or salt thereof and the quaternary ammonium salt in a weight ratio (the former: the latter) of 1: 0 to 1: 1. More preferably, it is contained in a ratio of 30: 1 to 4: 1. When the antibacterial composition contains the polyalkylene biguanide compound and / or salt thereof and the quaternary ammonium salt in such a weight ratio, the antibacterial effect is further improved.

  The antibacterial composition may further contain a general antibacterial component in addition to calcium oxide, the polyalkylene biguanide compound and / or salt thereof, and the quaternary ammonium salt as long as the characteristics of the present invention are not impaired. .

  The antibacterial composition may further contain a surfactant other than the quaternary ammonium salt. When the antibacterial composition further contains a surfactant other than the quaternary ammonium salt, the detergency and foaming properties are improved. Any appropriate surfactant can be used as the surfactant. Examples of the surfactant include other cationic surfactants (for example, primary to tertiary fatty amine salts, and 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium salts). An alkylbetaine type amphoteric surfactant (for example, N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine); an aminocarboxylic acid type amphoteric surfactant (for example, N, N-dialkylaminoalkylenecarboxylic acid); Alkylsulfobetaine-type amphoteric surfactants (eg, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine); imidazoline-type amphoteric surfactants (eg, 2-alkyl-1-hydroxyethyl-1-carboxy) Methyl imidazolinium betaine);

  The antibacterial composition may further include, for example, a water-soluble polymer, a chelating agent, an inorganic salt, a pigment, and / or a fragrance. Examples of the water-soluble polymer include gum arabic, carrageenan, sodium carboxymethylcellulose, hydroxycellulose, and sodium polyacrylate. Examples of the chelating agent include sodium ethylenediaminetetraacetate, tripolyphosphate, and hexametaphosphate. Examples of the inorganic salt include sodium chloride, potassium chloride, and sodium sulfate.

  The antibacterial composition is used as a disinfectant containing the antibacterial composition as it is or, for example, by adding any appropriate additive components (for example, various carriers, other surfactants, and antiviral components). Can do. The disinfectant can be provided in any suitable form. Examples of the form include liquid form, gel form, and powder form. When the form of the disinfectant is liquid, it can act on a wide range of disinfecting objects in a short time.

  The disinfectant can be provided as, for example, a lotion agent and a spray agent. The disinfectant can be used by filling a container, for example. Any appropriate container can be used as the container. Examples of the container include a bottle with a measuring cap, a trigger type spray container, and a pump spray container (for example, squeeze type and dispenser type pump spray containers). The disinfectant can be sprayed and / or sprayed, for example.

  Any appropriate amount of the disinfectant can be used. As said usage-amount, the quantity of the grade which the surface of the disinfection target object contacts the said disinfectant evenly is mentioned, for example. Arbitrary appropriate time can be employ | adopted as an action time with respect to the disinfection target of the said disinfectant. Examples of the action time include 5 minutes to 1 hour.

  The disinfectant can be used for any appropriate application. Such uses include, for example, disinfection of places where bacteria may be present and objects that may be contaminated with bacteria. More specifically, disinfection of facilities (eg, hospital rooms, living rooms, kitchens, bathrooms, toilets, and toilets) and furniture (eg, tables, chairs, and bedding), utensils (eg, tableware, cooking) Instrument and medical supplies), equipment, and disinfection of devices.

  Hereinafter, the components of the antibacterial composition will be specifically described.

[A-1. Calcium oxide]
The calcium oxide can take any suitable shape. Examples of the shape include particles. The particles can have any suitable average particle size. The upper limit of the average particle diameter is, for example, 10 μm, preferably 1 μm, more preferably 600 nm, and particularly preferably 300 nm. The lower limit of the average particle diameter is, for example, 10 nm. When calcium oxide has the above-described configuration, the antibacterial effect of the antibacterial composition is further improved.

The calcium oxide can take any suitable structure. An example of the structure is a porous body. The porosity of the calcium oxide can take any appropriate value. Specifically, the porosity is preferably 0.2cm ³ /g~1.2cm ³ / g, more preferably 0.4cm ³ /g~0.8cm ³ / g. Since calcium oxide has the above structure, a high specific surface area can be obtained, so that the antibacterial effect of the antibacterial composition is further improved.

  Any appropriate calcium oxide can be used as the calcium oxide. Examples of the calcium oxide include calcium oxide derived from natural materials and chemically synthesized calcium oxide. These can be used alone or in combination.

  The calcium oxide can be obtained by firing a material containing calcium carbonate. Any appropriate material can be used as the material. Examples of the material include natural materials containing calcium carbonate and chemically synthesized calcium carbonate. Examples of the natural material include biological materials and mineral materials. Examples of the biological material include corals, shells, eggshells, and fossils thereof. Any appropriate coral can be used as the coral. As said coral and its fossil, the coral containing calcium carbonate as a main component (for example, 50 weight% or more) and its fossil are mentioned, for example. Examples of the corals and their fossils include biological species belonging to the class of flower worms and their fossils. Examples of the biological species belonging to the class of flowering worms include biological species belonging to the hexagonal coral subclass (for example, biological species belonging to the order of Coralidae) and / or fossils thereof. Any appropriate shell can be used as the shell. Examples of the shell include scallop shells, oyster shells, hokki shells, clams shells, clams shells, tuna shells, abalone shells, and mussels shells. High safety can be achieved by using these biological materials. This is because the biological material-derived calcium has been approved for use as a food additive, and is a material with high safety established. Furthermore, a higher antimicrobial effect can be exhibited by using corals and their fossils. This is because corals and their fossils contain trace amounts of radioactive isotopes.

  Arbitrary appropriate temperature can be employ | adopted as a calcination temperature at the time of baking the material containing a calcium carbonate and obtaining the said calcium oxide. The firing temperature is, for example, 700 ° C or higher, preferably 900 ° C to 1500 ° C, and more preferably 1000 ° C to 1300 ° C. Firing may be performed in air or in an inert gas (for example, nitrogen gas). Any appropriate time can be adopted as the firing time. The firing time is, for example, 10 minutes to 10 hours, preferably 20 minutes to 5 hours, and more preferably 30 minutes to 2 hours. By calcination under the above conditions, the efficiency with which organic substances are thermally decomposed and removed, and the efficiency with which calcium carbonate is converted to calcium oxide are improved, and as a result, high antibacterial activity is obtained. Furthermore, it can be set as particulate calcium oxide by grind | pulverizing a baked product.

［化学式（１）中、Ｒ^ａは炭素数２〜８のアルキレン基を表し、ｎは２〜１８の整数を表す。］ [A-2. Polyalkylene biguanide compound]
The polyalkylene biguanide compound is represented by the chemical formula (1).

In Chemical Formula (1), ^{R a} represents an alkylene group having 2 to 8 carbon atoms, n is an integer of 2 to 18. ]

In the chemical formula (1), any appropriate chemical group can be used as the alkylene group having 2 to 8 carbon atoms represented by ^Ra . Examples of the alkylene group having 2 to 8 carbon atoms include a linear alkylene group and a branched alkylene group. Examples of the linear alkylene group include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group (hexamethylene group), a heptylene group (heptamethylene group), and an octylene group (octamethylene group). . Examples of the branched alkylene group include an isopropylene group, an isobutylene group, an isopentylene group, a dimethylpropylene group, and a dimethylbutylene group. When a linear alkylene group is used as the alkylene group having 2 to 8 carbon atoms, a stronger antibacterial effect can be obtained. When an alkylene group having 4 to 8 carbon atoms (for example, a hexamethylene group) is used as the alkylene group having 2 to 8 carbon atoms, a stronger antibacterial effect can be obtained. N in the chemical formula (1) is 2 to 18, preferably 10 to 14, and more preferably 11 to 13. When n is within the above range, the antibacterial effect and handleability are further improved.

  The antibacterial composition of the present invention contains the polyalkylene biguanide compound and / or a salt thereof. Any appropriate salt can be used as the salt. Examples of the salt include salts with inorganic acids (for example, hydrochloric acid, nitric acid, and sulfuric acid) and salts with organic acids (for example, acetic acid, lactic acid, and gluconic acid). As the salt, hydrochloride, acetate, and gluconate are preferable, and hydrochloride is most preferably used.

  The polyalkylene biguanide compound and / or salt thereof can be produced by any suitable production method. Examples of the production method include the method described in British Patent No. 702,268. A commercial product can be used as the polyalkylene biguanide compound and / or salt thereof. Examples of commercially available products include “Ecline Side BG” (manufactured by Riko Kyosan Co., Ltd.), “Proxel IB” (manufactured by Arch Chemicals), and “Lonza Back BG” (manufactured by Lonza Japan Ltd.). .

［化学式（２）中、Ｒ^１およびＲ^２はそれぞれ独立して、炭素数８〜１８のアルキル基を表し、Ｒ^３およびＲ^４はそれぞれ独立して、炭素数１〜４のアルキル基を表し、Ａ⁻は無機または有機の陰イオンを表す。］ [A-3. Quaternary ammonium salt]
The quaternary ammonium salt is represented by the chemical formula (2).

[In the chemical formula (2), R ¹ and R ² each independently represent an alkyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. , A ⁻ represents an inorganic or organic anion. ]

In the chemical formula (2), any appropriate alkyl group may be adopted as the alkyl group having 8 to 18 carbon atoms represented by R ¹ or R ² . As said alkyl group, a linear alkyl group and a branched alkyl group are mentioned, for example. Examples of the linear alkyl group include octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tetradecyl group (myristyl group), tetrahexyl group (palmityl group), and tetraoctyl group ( Stearyl group). Examples of the branched alkyl group include 1-methylheptyl group (sec-octyl group), 6-methylheptyl group (isooctyl group), 1,1-dimethylhexyl group, 2-ethylhexyl group, 1-methyltril group. Decyl group, 12-methyltridecyl group (isomyristyl group), 1-methylpentadecyl group, 14-methylpentadecyl group (isopalmityl group), 1-methylheptadecyl group, and 16-methylheptadecyl group (isostearyl group) Group). The number of carbon atoms of the alkyl group represented by R ¹ or ^{R 2,} preferably 8-15, more preferably 10-12.

In the chemical formula (2), any appropriate alkyl group may be adopted as the alkyl group having 1 to 4 carbon atoms represented by R ³ or R ⁴ . Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group (isopropyl group), a butyl group, a 1-methylpropyl group (sec-butyl group), and a 2-methylpropyl group (isobutyl group). And 1,1-dimethylethyl group (tert-butyl group). The number of carbon atoms of the alkyl group represented by R ³ or ^{R 4,} preferably 1 to 3, more preferably 1 to 2.

At least ^one of R ¹ and R ^{2 in} the chemical formula (2) may be a decyl group. Furthermore, both R ¹ and R ² can be a decyl group. At least one of R ³ and R ^{4 in} the chemical formula (2) may be a methyl group. Furthermore, both R ³ and R ⁴ can be methyl groups. When the quaternary ammonium salt has the above structure, the antibacterial effect is further improved.

In Chemical Formula (2), A ^- inorganic or organic anion represented by it may employ any suitable anion. Examples of the anion include halogen ions, inorganic acid ions, and organic acid ions.

  Examples of the halogen ion include chloride ion, bromine ion, and iodine ion. Examples of the inorganic acid ions include nitrate ions, sulfate ions, and phosphate ions. Examples of the organic acid ion include alkyl sulfate ion; monocarboxylic acid ion having 2 to 6 carbon atoms (for example, acetate ion, propionic acid ion, butyrate ion, and caproic acid ion); hydroxy having 3 to 6 carbon atoms. Carboxylate ions (eg, lactate, malate, and citrate); dicarboxylate (eg, oxalate, malonate, succinate, fumarate, maleate, and adipate) Is mentioned. Of these, halogen ions, sulfate ions, alkyl sulfate ester ions having 1 to 3 carbon atoms (for example, methyl sulfate ions), and dicarboxylate ions having 2 to 6 carbon atoms are preferable, and chloride ions and adipate ions are particularly preferable. .

  The quaternary ammonium salt can be produced by any suitable production method. Furthermore, a commercially available product can be used as the quaternary ammonium salt. Commercially available products include, for example, trade names “Cotamine D10P”, “Cotamine D86P”, and “Cotamine D2345P” (above, manufactured by Kao Corporation), trade names “Burdac 2280/2250”, and “Corboquart” ( As mentioned above, Lonza Japan Co., Ltd.), trade name “Cathogen DDM-PG” (Daiichi Kogyo Seiyaku Co., Ltd.), and trade names “Cation DDC-50” and “Osmoline DA-50” (Sanyo Kasei) Kogyo Co., Ltd.).

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. Unless otherwise specified, parts and percentages in the examples are based on weight.

[Example 1]
(Preparation of calcium oxide particles)
The coral coral was boiled with purified water for 1 hour for sterilization and washing, and then water was dried. Subsequently, a coarse coral powder having an average particle size of about 5 mm was obtained by coarse pulverization. The coral coarse powder was baked for 1 hour at 1150 ° C. using an electric kiln. The coral coarse powder after firing was further pulverized using a fine pulverizer to obtain coral-derived calcium oxide particles having an average particle diameter of about 100 nm.

(Preparation of antibacterial composition A)
Polyhexamethylene biguanide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the polyalkylene biguanide compound and / or salt thereof. Didecyldimethylammonium hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the quaternary ammonium salt. Each component was added to purified water in the proportions shown in Table 1 to prepare antibacterial composition A. In addition, pH of the antimicrobial composition A was set to 11.5 by adding sodium hydroxide suitably.

(Antimicrobial test)
The test bacteria (Bacillus cereus NBRC13494 strain) was enriched as usual. 1 mL of the enriched bacterial cell solution was inoculated into 10 mL of the antibacterial composition A, and allowed to stand at 30 ° C. for 30 minutes to prepare a sample. After standing, 1 mL of the above sample was inoculated into two standard agar media and cultured at 36 ° C. for 24 hours, and the number of colonies was measured. The measured value (CFU / mL) of the number of colonies on the two standard agar media was defined as measured value 1 and measured value 2, respectively. The results are shown in Table 2. Furthermore, the average value (CFU / mL) of the measured value 1 and the measured value 2 is shown in Table 2 as an average value.

[Comparative Example 1]
An experiment was conducted in the same manner as in Example 1 except that the purified water was used instead of the antibacterial composition A in Example 1, and the bacterial cell solution enriched in Example 1 was used. The results are shown in Table 2.

  Furthermore, the average value of the measured value 1 and the measured value 2 in Comparative Example 1 was taken as 100%, and the residual rate (%) of the bacterial cells in Example 1 was determined. The results are shown in Table 2.

  As shown in Table 2, it was found that the antibacterial composition A has an extremely high antibacterial action.

  The antibacterial composition of the present invention has further improved antibacterial action and further improved safety. Therefore, the antibacterial composition of the present invention can be particularly suitably used for disinfection of, for example, facilities, furniture, instruments, equipment, and devices.

Claims (4)

With calcium oxide;
An antibacterial composition comprising: a polyalkylene biguanide compound having a structure represented by the chemical formula (1) and / or a salt thereof.

In Chemical Formula (1), ^{R a} represents an alkylene group having 2 to 8 carbon atoms, n is an integer of 2 to 18. ]   The antibacterial composition according to claim 1, wherein the calcium oxide is in the form of particles having an average particle size of 10 μm or less.   The antibacterial composition according to claim 1 or 2, wherein the calcium oxide is obtained by baking a biological material containing calcium carbonate. The antibacterial composition according to any one of claims 1 to 3, further comprising a quaternary ammonium salt having a structure represented by the chemical formula (2).

[In the chemical formula (2), R ¹ and R ² each independently represent an alkyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. , A ⁻ represents an inorganic or organic anion. ]