JP2012031117A - Antibacterial composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble sterilization/antibacterial agent which has antibacterial activity and antifungal activity in a wide range, and is suppressed in discoloring and coloring caused by an ultraviolet ray or the like, and excellent in light resistance.SOLUTION: This antibacterial composition contains one or more compounds of the silver salt or silver complex of 2H-pyran-2-one-4, 6-dicarboxylic acid or the derivative thereof, and creatinine. A molar ratio (B)/(A) of creatinine (B) to silver (A) in the compound is 2 to 80. By adding the antibacterial composition to a bacteria remover or a deodorant, a cleaning agent, paint, a bonding agent of an adhesive agent, and a fiber antibacterial treatment agent, these items are expected to be imparted with antibacterial properties.

Description

  The present invention relates to an antibacterial composition and its use, and more particularly to an antibacterial composition having a wide range of antibacterial and antifungal activities and capable of suppressing discoloration and coloring caused by ultraviolet irradiation and use thereof.

  In recent years, bactericides, antibacterial agents, preservatives and the like using silver ions have been developed and are widely used in daily necessities. Among those using silver ions, there are those in which the actual effect is suspected and those that cannot be used at a concentration that achieves a desired effect because of low water solubility. Then, it is known that silver ions are generally reduced by ultraviolet rays and altered. In particular, when an antibacterial agent or antibacterial agent containing silver ions is applied to an object and dried and solidified, the object is often contaminated by discoloration, coloring, metallic silver deposition, or the like.

  As a bactericidal / antibacterial agent component that maintains high antibacterial activity and has low toxicity, skin irritation and mucosal irritation, complexes of silver and imidazoles are known (Patent Documents 1 to 4). These complexes have a problem that they are hardly soluble in water and have low photostability.

  It has been found that complexes of silver with pyrrolidonecarboxylic acid, histidine and the like are water-soluble and stable (Patent Documents 5 to 8 and Non-Patent Document 1). These complexes also cannot be stably present for a long time in a state dissolved in water, and cause precipitation of metal silver and severe discoloration. The discoloration of the silver complex itself also caused discoloration of the object to be added, limiting the applicable objects.

  A composition (Patent Documents 9 and 10) containing an inorganic supported silver antibacterial agent and purine, pyrimidine bases, thiabendazole and the like has been proposed. These compositions have poor water solubility, and it has been difficult to effectively use silver ions.

  A silver complex (Patent Document 11) having a ligand of 5,5-disubstituted hydantoin, barbituric acid or the like has also been devised. In order to use silver ions as an aqueous solution, it is necessary to add a 1 molar equivalent of a ligand to silver and further adjust the basicity. Nevertheless, a sufficient discoloration suppressing effect cannot be obtained.

  2H-pyran-2-one-4,6-dicarboxylic acid (hereinafter referred to as PDC), alkali metal salts and esters thereof are high safety and are effective components of antibacterial agents and bactericides with little environmental impact. The use is expected (Patent Documents 12 and 13). It is also known that PDC silver has antibacterial properties (Patent Document 14). However, as will be described later, PDC silver is inferior in light resistance in that it causes discoloration or coloring due to ultraviolet rays or the like.

WO95 / 007913 JP 11-077912 JP2005-145923 JP 2009-001636 A JP 2000-256365 A JP 2000-016905 A JP 2001-335405 A JP2008-285543 JP 2003-176220 A JP 2003-192918 A WO2002 / 026039 Republished Patent 2008/078723 JP 2009-234594 A WO2009 / 151146

Molecular design and synthesis of water-solvable silver (I) complexes exhibiting a wide spectrum of effective antimicrobials. Kenji N. , Isao A. , Noriko C.I. K. Takako K .; 2008, Current Topics in Biochemical Research. , 10, 1, p1-11.

  Therefore, an object of the present invention is to provide an antibacterial composition having a wide range of antibacterial and antifungal activities and excellent in light resistance that suppresses discoloration and coloring due to ultraviolet rays and the like.

  As a result of intensive studies to achieve the above object, the present inventors have formulated a certain amount of creatinine into one or more of the silver salt or silver complex of PDC and the silver salt or silver complex of its derivative. The present inventors have found that an antibacterial composition having a broad spectrum of antibacterial and antifungal properties, good water solubility, and capable of suppressing discoloration, coloring, and precipitation due to ultraviolet rays can be produced. . That is, the present invention is an antibacterial agent containing a silver salt or silver complex of 2H-pyran-2-one-4,6-dicarboxylic acid, one or more compounds of silver salts or silver complexes of derivatives thereof, and creatinine. Provided is the antibacterial composition, wherein the molar ratio (B) / (A) of silver (A) to creatinine (B) in the compound is 2 to 80 To do. In the present specification, “a derivative of 2H-pyran-2-one-4,6-dicarboxylic acid” means a monoester or monoamide of 2H-pyran-2-one-4,6-dicarboxylic acid. To do.

  The present invention also provides a disinfectant or deodorant containing the antibacterial composition.

  The present invention also provides a cleaning agent containing the antibacterial composition.

  The present invention also provides a paint containing the antibacterial composition.

  The present invention also provides an adhesive or pressure-sensitive adhesive containing the antibacterial composition.

  The present invention also provides a fiber antibacterial processing agent containing the antibacterial composition.

  According to the antibacterial composition of the present invention, in which one or more compounds of PDC silver salt or silver complex, silver salt or silver complex of PDC, and creatinine are blended at a certain ratio, Light resistance to ultraviolet rays and the like is obtained. Utilizing this characteristic, the antibacterial composition of the present invention is a disinfectant, deodorant, detergent, cosmetic, paint, adhesive or pressure-sensitive adhesive, antibacterial fiber treatment agent, pharmaceutical and quasi-drug, Expected to be used for food.

The antibacterial composition of the present invention contains, as essential components, one or more compounds of PDC silver salt or silver complex, a silver salt or silver complex thereof, and creatinine. PDC has the following chemical formula:
The silver salt or silver complex of PDC or a derivative thereof is a compound in which at least one carboxyl group contained in PDC or a derivative thereof is bonded to a silver ion. In the present specification, one in which one silver ion is bonded to PDC is referred to as PDC mono-silver, and two silver ions bonded to one is referred to as PDC disilver.

  The silver salt or silver complex of PDC or a derivative thereof may be a double salt formed by a part of 2H-pyran-2-one ring of two or more PDCs or a derivative thereof and one or more silver ions.

  The silver salt or silver complex used in the present invention may be the above PDC monosilver, a monosilver salt or monosilver complex thereof, a PDC disilver, or a double salt of PDC or a derivative thereof. May be used in combination of two or more.

  For example, according to the production method described in JP-A-2009-082064, PDC introduces PDC fermentation production plasmids pCDFDuet-cutC and pULABC into E. coli XL1-Blue strain (STRATEGENE, CA, USA) using saccharides as a starting material. It is obtained by culturing the transformed cells.

  A silver salt or silver complex of PDC or a derivative thereof is obtained by dissolving or dispersing a silver salt such as silver nitrate, silver carbonate, silver sulfate or silver oxide in an aqueous medium such as water or alcohol, and further adding PDC or It can be obtained by acting the derivative. The obtained silver salt or silver complex of PDC or a derivative thereof is purified by recrystallization, filtration, drying or the like as appropriate.

Creatinine, another essential component of the antibacterial composition of the present invention, has the following chemical formula:
It is a water-soluble compound having a molecular weight of 113.12.

  The antibacterial composition of the present invention can be obtained by adding one or more compounds of PDC silver salt or silver complex, silver salt or silver complex thereof and creatinine to an aqueous medium. Alternatively, PDC and / or a derivative thereof and creatinine may be added to the aqueous medium, and then a silver compound such as silver nitrate or silver oxide or a solution thereof may be added. Further, a silver compound such as silver nitrate or silver oxide may be further added to an aqueous medium to which creatinine is added, and then PDC and / or a derivative thereof may be added to the solution. Examples of the aqueous medium include water, a mixture of water and an organic medium such as alcohol, and preferably water.

  The antibacterial composition of the present invention comprises a molar ratio (B) of silver (A) and creatinine (B) in any one or more of a silver salt or silver complex of PDC or a silver salt or silver complex of a derivative thereof. ) / (A) is 2 to 80, preferably 3 to 80, more preferably 3 to 10, and particularly preferably 3 to 8. When the molar ratio is less than 2, the light resistance of the antibacterial composition in the dissolved state and / or dryness is not improved, and the antibacterial composition cannot be prepared at a high concentration because the solubility decreases. There's a problem. If the molar ratio is too high, cost increases due to an increase in the concentration of creatinine and solubility of creatinine becomes a problem. Accordingly, the upper limit is a molar ratio of 80.

  The antibacterial composition of the present invention has a wide range of antibacterial and antifungal activities. Specifically, gram-positive cocci such as staphylococci, methicillin-resistant Staphylococcus aureus, streptococci, grams such as Bacillus, Clostridium, Corynebacterium, Listeria, Propionibacterium or Actinomyces Gram-positive bacteria such as positive gonococci; Gram-negative cocci such as Neisseria or Blanchamella, Pseudomonas, Escherichia coli, Enterohemorrhagic Escherichia coli, Salmonella, Shigella, Pesto, Haemophilus, Brucella or Bordetella Gram-negative bacteria such as negative gonococci: spiral gonococci such as Vibrio; Rickettsia: chlamydia; mycoplasma and the like. Examples of fungi include yeasts such as Candita; molds such as Aspergillus, Cladosporium and Trichophyton. In particular, Staphylococcus aureus subspecies Aureus, Escherichia coli, Pseudomonas aeruginosa, Salmonella enteritidis, Vibrio parahaemoliticus, Aspergillus niger, Candida albicans, Cladospodium cladospolio Effective for Ides, Trichophyton Rubulum, etc.

  In order for the antibacterial composition of the present invention to exhibit antibacterial and bactericidal properties, although depending on the bacterial species, the lower limit of the content of PDC and / or its derivative or silver is usually 0.005 mM or more. , Preferably 0.01 mM or more, particularly preferably 0.04 mM or more. If the content is too low, sufficient antibacterial and bactericidal properties cannot be obtained. Moreover, the upper limit of the content of PDC and / or its derivative or silver is usually 150 mM or less, preferably 50 mM or less, particularly preferably 20 mM or less. If the content is too high, insoluble materials may be produced.

  The antibacterial composition of the present invention has a pH of usually 1 to 12, preferably 3 to 6.

  In the antibacterial composition of the present invention, in addition to the above essential components, auxiliary agents widely used in the antibacterial agent / bactericide field can be used as long as the effects of the present invention are not inhibited. Examples of such auxiliaries include known antibacterial and antifungal agents, chelating agents, pH adjusters, surfactants, ultraviolet absorbers, antioxidants, emulsifiers, fragrances, colorants, water-soluble polymers, Examples include alcohols, fluorescent brighteners, viscosity modifiers, and foaming agents.

  The antibacterial composition of the present invention can be used in the form of a solution, spray, cream, paste, gel, gel, powder, granule and the like. Since the composition of the present invention is water-soluble, it is particularly advantageous to use it as an aqueous solution or spray.

  The antibacterial composition of the present invention can be used for disinfectants, deodorants, detergents, cosmetics, paints, adhesives or adhesives, textile antibacterial agents, pharmaceuticals and quasi drugs, foods, feeds, agricultural chemicals, etc. It can be added as an antibacterial bactericidal active ingredient. Even if it uses for the said use, the antimicrobial composition of this invention exhibits the outstanding light resistance. The compounding amount of the antibacterial composition of the present invention in the above-mentioned use is usually 0.005 to 100 mM, preferably 0.01 to 10 mM, particularly preferably as the content of PDC and / or a derivative thereof or silver. 0.04 to 4 mM.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention. However, the present invention is not limited to the following examples.

[Preparation Example 1] Preparation of PDC silver According to the method described in JP2009-082064A. PDC was extracted after culturing a transformed cell in which PDC fermentation production plasmids pCDFDuet-qutC and pULABC were introduced into E. coli XL1-Blue strain (STRATEGENE, CA, USA) using glucose as a starting material.

  1.03 g (5.50 mmol) of PDC obtained above was dissolved in 37.5 ml of water. To this aqueous solution, 12.5 ml of an aqueous solution of 0.85 g (5.00 mmol, Sigma-Aldrich Japan Co.) of silver nitrate was added to obtain a white precipitate of PDC monosilver. The precipitate was collected by filtration, and the collected product was dried. Similarly, PDC disilver was synthesized using 0.92 g (5.00 mmol) of PDC and 1.87 g (11.0 mmol) of silver nitrate.

[Examples 1 and 2 and Comparative Examples 1 to 3]
1. Preparation of antibacterial composition containing PDC silver and creatinine 0.100 g (0.324 mmol) of PDC monosilver obtained in Preparation Example and 0.146 g (1.30 mmol, Wako Pure Chemical Industries, Ltd.) of creatinine in 100 ml of water To obtain a composition having a silver concentration of 3.24 mM and a creatinine / silver molar ratio of 4 (Example 1). Further, except that PDC monosilver (0.324 mmol) is changed to 0.670 g (0.162 mmol) of PDC disilver, the silver concentration is 3.24 mM and the creatinine / silver molar ratio is 4 in the same manner as in Example 1. A composition (Example 2) was prepared.

2. Antibacterial test of antibacterial composition (1)
In order to confirm the antibacterial effect of the antibacterial composition, the following bacterial species:
(Bacteria)
1. Staphylococcus aureus subsp. Aureus, NBRC13276,
2. E. coli (Escherichia coli, NBRC 3972), and
(fungus)
1. Aspergillus niger (NBRC 9455)
MIC (minimum growth inhibitory concentration) was measured.

  For comparison, the same measurement was performed for silver nitrate, which has been conventionally known as an antibacterial agent. Specifically, 0.055 g (0.324 mmol) of silver nitrate was dissolved in 100 ml of water and used (Comparative Example 1; silver concentration: 3.24 mM). Moreover, in order to compare the effect of creatinine addition, Comparative Example 2 and Comparative Example 3 (all silver concentration: 3.24 mM) were prepared by the same method as Example 1 and Example 2 except not containing creatinine.

The measurement test of the growth inhibitory concentration was performed according to the following procedure according to the MIC (minimum growth inhibitory concentration) agar plate dilution method by the Japanese Society of Chemotherapy. The bacteria were cultured overnight at 37 ± 3 ° C. on Muller Hinton II agar medium (Becton Dickinson). The fungi were cultured at 25 ± 3 ° C. for 5 to 10 days in a Sabouraud-glucose agar medium (Nissui Pharmaceutical Co., Ltd.). The test cells on the agar plate were washed with sterilized physiological saline using MacFarland No. 1 (bacteria were about 10 ⁸ cfu / mL, fungi were about 10 ⁶ cfu / mL) and suspended in a turbidity to obtain a bacterial solution for inoculation.

  Example 1 and Comparative Example 1 were each sterilized through a membrane filter (product name: Milex HV, manufactured by Nihon Millipore Corporation).

  Using a sensitivity measurement medium kept at about 45 ° C (bacterial is Mueller Hinton II agar medium, fungus is Sabouraud glucose agar medium), prepare 2 double drug series each with a maximum concentration of 10%. What was solidified in a sterile petri dish was used as a test substance-containing sensitive medium. As a control, one using each sterilized purified water instead of the drug stock solution was prepared in the same manner to prepare a drug-free medium.

  On the surface of the agar medium containing the test substance-containing sensitive medium and the drug-free medium, the inoculum was smeared with a platinum loop for about 2 cm (n = 2 for the test substance-containing sensitive medium, n = for the drug-free medium). 1). The bacteria were aerobically cultured at 37 ± 3 ° C. for 18 to 20 hours, and the fungi were cultured at 25 ± 3 ° C. for 3 to 5 days. After culture, the presence or absence of bacterial growth was determined for each test substance-containing sensitive medium and drug-free medium. Table 1 shows the MIC value (silver concentration that inhibits the growth of bacteria) calculated from these measurement results.

3. Antibacterial test of antibacterial composition (2)
In order to further confirm the antimicrobial effect of the antimicrobial composition of the present invention, the following fungi:
Black mold (Cladosporium cladosporoides JCM 3899)
MIC (minimum growth inhibitory concentration) was measured. For comparison, the same measurement was performed for Comparative Example 1 (silver nitrate 3.24 mM), Comparative Example 2 (PDC monosilver 3.24 mM) and Comparative Example 3 (PDC disilver 1.62 mM).

First, the strain was cultured at 25 ± 3 ° C. for 5 to 10 days on PDA agar medium (Becton Dickinson). The test bacterial cells on the agar plate were sterilized with purified water, and MacFarland No. The suspension was suspended in a turbidity equivalent to 1 (about 10 ⁶ cfu / mL) to obtain a bacterial solution for inoculation.

  The antibacterial compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were each sterilized through a membrane filter (product name: Milex HV, manufactured by Nihon Millipore Corporation) having a pore diameter of 0.45 μm.

  Using a sensitivity measurement medium (PDA agar medium) maintained at about 45 ° C., two double-dilute drug series each with a maximum concentration of 10% were prepared and solidified in a sterilized petri dish. A medium was used. As a control, one using each sterilized purified water instead of the drug stock solution was prepared in the same manner to prepare a drug-free medium.

  On the surface of the agar medium containing the test substance-containing sensitive medium and the drug-free medium, the bacterial solution for inoculation was smeared with a platinum loop about 2 cm (n = 2). Aerobic culture was performed at 25 ± 3 ° C. for 3 to 5 days. After the culture, the presence or absence of bacterial growth was determined for each test substance-containing sensitive medium and drug-free medium, and the MIC value was determined (Table 2).

  From the results of Tables 1 and 2, it was confirmed that the antibacterial composition of the present invention has an excellent antibacterial effect against a wide range of bacteria and fungi, like silver nitrate and PDC silver.

4). Light resistance test of antibacterial composition The light stability of the antibacterial composition of the present invention was confirmed in a solution and in a dry state.

(1) Light Resistance Test in Solution State Examples 1 and 2 and Comparative Examples 2 and 3 were passed through a membrane filter (product name: Milex LG, manufactured by Nippon Millipore Corporation) with a pore size of 0.20 μm, respectively. Removed. Next, 10 ml of each solution was placed in a glass vial (20 ml capacity) and placed under a high energy ultraviolet light source without a lid. As a light source, a sterilization lamp GL-15 (sterilization line output 4.9 W, ultraviolet radiation intensity 51 μW / cm ² ) manufactured by Toshiba Lighting & Technology Co., Ltd. was used. The distance between the light source and the solution (liquid level) was 4 cm. Whether or not discoloration or precipitation occurred in each solution every 12 hours was observed according to the following criteria. The results are shown in Table 3.
○: No discoloration or precipitation was observed.
X: Discoloration or generation of precipitates was observed.

(2) Light resistance test in a dry state 0.05 ml of each solution was dropped on a slide glass, and volatile components were removed at 50 ° C. under reduced pressure to obtain a dried test specimen. The test body was placed under the ultraviolet light source (distance between the light source and the test body: 6 cm). Discoloration up to 60 minutes was observed according to the following criteria. The results are shown in Table 3.
☆: Transparent ◎: Translucent ○: White ×: Colored yellow, brown, gray, black, etc.

  From the results in Table 3, in Comparative Examples 2 and 3 using only PDC silver, the light resistance in the solution state was inferior. On the other hand, the composition of Example 1 and 2 which mix | blended PDC silver and creatinine had the outstanding light resistance in the solution state and the dryness state.

[Comparative Examples 4 to 8]
In Example 1, instead of creatinine, the chemical formula:
Guanine represented by the chemical formula:
Acetylacetone guanidine represented by the chemical formula:
5-azacytosine represented by the chemical formula:
Hydantoin represented by the chemical formula:
A composition was obtained in the same manner as in Example 1 except that 5,5-dimethylhydantoin represented by the formula (1) was added. Here, the molar ratio of silver in the PDC single silver to the above compound was set to 4 as in Example 1. Table 4 shows the results of the light resistance test.

  In Comparative Examples 4, 5 and 6, as shown in Table 4, the composition could not be completely dissolved in water and could not be evaluated. Moreover, in Comparative Examples 7 and 8, although dissolved, the light resistance in the solution state deteriorated after 1 day, and the light resistance in the dry state was not recognized.

[Examples 3 to 9, Comparative Example 9] Creatinine Blending A composition was prepared in the same manner as in Example 1 except that the creatinine blending amount in Example 1 was changed as shown in Table 5. Table 5 shows the results of the light resistance test of each composition.

  From Table 5, the creatinine addition amount with respect to PDC monosilver shows the discoloration inhibitory effect in 2-80 molar equivalent with respect to silver, 3-80 molar equivalent is appropriate, and 3-8 molar equivalent is optimal. confirmed.

[Examples 10 to 11 and Comparative Examples 10 to 11] Disinfectant using antibacterial composition In Example 1, the same procedure as in Example 1 was used except that the concentrations of PDC silver and creatinine were increased 5 times. A composition was prepared to obtain a composition having a PDC monosilver concentration of 16.2 mM and a creatinine / silver molar ratio of 4 (Example 10). Similarly, a composition was prepared in the same procedure as in Comparative Example 2 except that the concentration of PDC monosilver was 5 times in Comparative Example 2, and a composition containing no creatinine at a PDC monosilver concentration of 16.2 mM (Comparison Example 10) was obtained.

  By adding 20 ml of the composition of Example 10 to 80 ml of general-purpose 99.5% ethanol as a disinfecting / deodorizing agent, a disinfectant having a PDC monosilver concentration of 3.24 mM (Example 11) was prepared. Similarly, 20 ml of the composition of Comparative Example 10 was added to 80 ml of 99.5% ethanol to prepare a disinfectant (Comparative Example 11) having a PDC monosilver concentration of 3.24 mM.

  The disinfectant of Example 11 was left at room temperature in a sealed state in a transparent glass container, and the appearance was observed. After 7 days, no discoloration or precipitation was observed in the disinfectant. Therefore, the stability of the disinfectant was confirmed.

(Light resistance test in solution)
10 ml of the disinfectant of Example 11 and Comparative Example 11 were each placed in a 20 ml glass vial and placed under the ultraviolet light source (distance between the light source and the liquid surface: 4 cm) without a lid. Whether or not discoloration or precipitation occurred after 10 minutes was observed according to the following criteria. The results are shown in Table 6.
○: No change ×: Discoloration or precipitation XX: Significant discoloration or precipitation

(Stability test after drying)
0.05 ml of the disinfectant of Example 11 and Comparative Example 11 was dropped on a slide glass and left at room temperature for 1 day to obtain a dry test body from which volatile components were removed. This test specimen was left for another 3 days at room temperature, and the color change was observed according to the following criteria. The results are shown in Table 6.
○: No discoloration ×: Discoloration

  From Table 6, it was confirmed that the disinfectant containing the antibacterial composition of the present invention has excellent light resistance.

(Sterilization performance test)
The disinfectant of Example 11 was sprayed on a coated steel plate at 0.1 g / 25 cm ² . After 1 hour and 7 days after spraying at room temperature, the number of viable bacteria on the coated steel plate was counted using an environmental microorganism testing reagent (product name: Petan Check (registered trademark) 10, manufactured by Eiken Science Co., Ltd.). For comparison, 99.5% ethanol was evaluated in the same manner as in Example 11 (Comparative Example 12). The results are shown in Table 7.

  From Table 7, the number of viable bacteria after 7 days was less than the condition of unsprayed and sprayed with ethanol alone. Therefore, it was confirmed from only ethanol (Comparative Example 12) that the disinfecting performance of the disinfecting agent is persistent.

[Example 12, Comparative Example 13] Detergent using antibacterial composition 20 ml of the composition of Example 10 was added to 80 ml of a commercially available liquid synthetic detergent (product name: Top NANOX, manufactured by Lion Corporation). Thus, a cleaning agent having a silver concentration of 3.24 mM was prepared (Example 12). Similarly, a detergent having a silver concentration of 3.24 mM was prepared by adding 20 ml of the composition of Comparative Example 10 to 80 ml of the liquid synthetic detergent (Comparative Example 13).

  The cleaning agent of Example 12 was allowed to stand at room temperature in a sealed state with a transparent glass container, and the appearance was observed. Seven days later, since no discoloration or precipitation was observed in the cleaning agent, the stability of the cleaning agent was confirmed.

  For the cleaning agents of Example 12 and Comparative Example 13, a light resistance test and a stability test were performed in the same manner as in Example 11. The results are shown in Table 8.

  From Table 8, it was confirmed that the detergent containing the antibacterial composition of the present invention has excellent light resistance.

  The cleaning agent of Example 12 was diluted 3,000 times with water to obtain a washing liquid. 300 ml of this washing liquid was put into a 1000 ml Erlenmeyer flask together with an 8 cm × 8 cm cotton cloth. The flask was rotated and stirred, followed by 5 minutes of washing followed by 2 minutes of rinsing twice. The taken-out cotton cloth was naturally dried at room temperature. After drying, the cotton fabric was observed to be colored. No color was observed on the washed cotton fabric.

[Example 13, Comparative Example 14] Paint using antibacterial composition By adding 20 ml of the composition of Example 10 to 80 ml of a commercially available synthetic resin paint (product name: aqueous versatile, manufactured by Asahi Pen Co., Ltd.) A paint having a silver concentration of 3.24 mM was prepared (Example 13). Similarly, a paint having a silver concentration of 3.24 mM was prepared by adding 20 ml of the composition of Comparative Example 10 to 80 ml of the synthetic resin paint (Comparative Example 14).

  The paints of Example 13 and Comparative Example 14 were allowed to stand at room temperature for 5 days in a sealed state with a transparent glass container, and the appearance was observed. Although the paint of Comparative Example 14 was browned, no discoloration or precipitation was observed in the paint of Example 13.

The coating material of Example 13 was applied to MDF (medium fiber board) at 0.014 ml / cm ² and left at 20 ° C. for 2 hours to cure the coating material. No change in hue was observed in the coated film after painting.

[Example 14, Comparative Example 15] Adhesive using antibacterial composition Commercially available specially modified vinyl acetate / acrylic copolymer emulsion adhesive (product name: VW-H-135, manufactured by J-Chemical Co., Ltd.) An adhesive having a silver concentration of 3.24 mM was prepared by adding 20 ml of the composition of Example 10 to 80 ml (Example 14). Similarly, an adhesive having a silver concentration of 3.24 mM was prepared by adding 20 ml of the composition of Comparative Example 10 to 80 ml of the emulsion adhesive (Comparative Example 15).

  The adhesive of Example 14 was allowed to stand at room temperature in a state of being sealed with a transparent glass container, and the appearance was observed. Seven days later, since no discoloration or precipitation was observed in the adhesive, stability was confirmed.

  With respect to the coating materials of Example 14 and Comparative Example 15, a light resistance test and a stability test were performed in the same manner as in Example 11. The results are shown in Table 9.

  From the results in Table 9, it was confirmed that the adhesive containing the antibacterial composition of the present invention has excellent light resistance.

3% by weight of the cross-linking agent (product name: K-132D, manufactured by J-Chemical Co., Ltd.) was added to the adhesive of Example 14 and mixed, and the mixture was applied to MDF at 65 g / m ² . The olefin film was adhered to the coated surface at 20 ° C. under a pressure condition of 4 kgf / cm ² × 20 minutes. Then, the immersion peeling test was implemented. As a result, the same adhesive strength as that obtained by adding water instead of the antibacterial composition was exhibited.

[Example 15, Comparative Example 16] Fiber antibacterial processing agent using antibacterial composition An antibacterial processing agent was prepared by diluting the composition of Example 1 20 times with water (Example 15). Similarly, the composition of Comparative Example 2 was diluted 20 times with water to prepare an antibacterial processing agent (Comparative Example 16). An 8 cm × 8 cm cotton cloth was dipped in a beaker containing the treatment agent of Example 15 or Comparative Example 16, so that about 0.8 g of the antibacterial processing treatment agent was adhered thereto, and dried in a dryer at 105 ° C.

The above-described cotton treated with antibacterial treatment was placed under the ultraviolet light source (distance between the light source and the test piece: 6 cm). The color change after 30 minutes was observed according to the following criteria.
○: No discoloration ×: Discoloration

  From Table 10, it was confirmed that the cotton cloth which gave the antibacterial processing with the fiber processing agent containing the antibacterial composition of this invention has the outstanding light resistance.

Claims (6)

  A silver salt or silver complex of 2H-pyran-2-one-4,6-dicarboxylic acid, a silver salt or silver complex of a derivative thereof, and an antibacterial composition containing one or more compounds and creatinine, The antibacterial composition, wherein a molar ratio (B) / (A) of silver (A) to creatinine (B) in the compound is 2 to 80.   A disinfectant or deodorant containing the antibacterial composition according to claim 1.   A cleaning agent comprising the antibacterial composition according to claim 1.   A paint containing the antibacterial composition according to claim 1.   An adhesive or pressure-sensitive adhesive containing the antibacterial composition according to claim 1.   A fiber antibacterial processing agent containing the antibacterial composition according to claim 1.