JP5377003B2 - Antibacterial agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antimicrobial agent that is clear and colorless, does not discolor by an ultraviolet light and has excellent stability, antimicrobial property, antiseptic property and antifungal performance. <P>SOLUTION: The antimicrobial agent is obtained by dissolving silver oxide and phytic acid in an aqueous solvent, and contains at least one chelating reagent selected from ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an antibacterial agent that utilizes the antibacterial effect of silver ions and is used in cosmetics, quasi drugs, pharmaceuticals, and other miscellaneous goods.

  In this type of conventional application field, parabens (paraoxybenzoic acid esters) are often used as preservatives. However, due to the impact of safety on humans, research on antibacterial, antiseptic and antifungal agents other than parabens has been promoted, and phenoxyethanol and the like may be used as an alternative. Although this phenoxyethanol is less toxic than parabens, it has a disadvantage that it must be added in a large quantity because of its weak antibacterial properties. For example, in the case of cosmetics, if the antibacterial, antiseptic and antifungal agents as described above are not used, the active ingredients of the cosmetics rot immediately, so the amount of the active ingredients must be low.

  In addition, as an antibacterial agent using silver, phytic acid, silver nitrate, polyacrylic acid as disclosed in Patent Document 1, or phytic acid, silver as disclosed in Patent Document 2 are disclosed. The thing containing the carboxylate of this etc. is known.

Japanese Patent Laid-Open No. 01-12531 JP 2004-2227 A

  The above-mentioned antibacterial, antiseptic and antifungal agents including parabens have some concerns regarding safety and antibacterial, antiseptic and antifungal performance. Therefore, products with excellent safety, antibacterial, antiseptic, and antifungal performances are faced. Moreover, the antibacterial agent using silver mentioned above shows discoloration by ultraviolet rays in the antibacterial agent stock solution. Therefore, normally, an ultraviolet irradiation device is required to carry out ultraviolet irradiation at the time of manufacture of the antibacterial agent and sufficiently change the color before shipping, which requires manufacturing time and labor costs required for manufacturing. When shipping without UV irradiation or discoloration, light must be kept away from the use of light-shielding bottles during transportation, storage, and preparation. That is, it cannot be stored for a long time without actually changing color. When this antibacterial agent using silver is mixed with an active ingredient such as a deodorant or cosmetic, precipitation reaction or discoloration may be observed. This is because the silver and the active ingredient or other mixed components in the antibacterial agent cause a chemical reaction and the stability is lost. In such a case, it is impossible to mix the antibacterial agent using silver and the active ingredient, and it is not a product, or precipitation is reduced by reducing the concentration of deodorant, active ingredient or antibacterial agent. However, at the same time, the deodorizing power and the unique effects such as cosmetics and the antibacterial, antiseptic and antifungal effects are also reduced.

  An object of the present invention is to solve such problems, and to provide an antibacterial agent which is colorless and transparent and does not cause discoloration due to ultraviolet rays and has excellent stability, antibacterial, antiseptic and antifungal properties.

The antibacterial agent according to claim 1 of the present invention is characterized by dissolving silver oxide and phytic acid in an aqueous solvent and containing a chelating agent.
The antibacterial agent according to claim 2 is characterized in that the chelating agent is at least one selected from ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid.

As described above, according to the antibacterial agent of the present invention, the following effects can be obtained.
It was found that antibacterial agents containing phytic acid and high concentrations of silver nitrate and carboxylate are very likely to be discolored by ultraviolet rays, but antibacterial agents in which silver oxide is dissolved with an acid are less likely to discolor. Silver oxide has a low solubility and hardly dissolves in water, but dissolves in an acid and easily dissolves in a strong acid solution. In particular, phytic acid is a strong acid and has an effect of appropriately increasing the stability of the antibacterial agent. In addition, phytic acid is known to have an effect of enhancing the storage stability of foods, and is a component derived from rice bran, which is preferable from the viewpoint of safety. The addition rate of the antibacterial agent is usually a very small amount of 0.05% to 1%, and in the case of a composition that dislikes moisture, the lower the addition rate, the more practical. In addition, it is preferable to dilute a high-concentration product so that the transportation cost, the management cost, the labor cost required for storage, the storage cost, etc. can be reduced. Therefore, there is a need to increase the silver concentration of the antibacterial agent stock solution. Antibacterial agents containing phytic acid and high concentrations of silver nitrate and carboxylate change from colorless and transparent to light pink and purple to amber when irradiated with ultraviolet light. Antibacterial agents containing conventional phytic acid and high concentrations of silver nitrate and carboxylate are also used well in general low-reactivity compositions and low concentrations as general industrial raw materials, and in areas where discoloration is not an issue it can. However, discoloration can be a very serious problem in cosmetics and other consumer products and high value-added products. The antibacterial agent containing this conventional phytic acid and silver nitrate or carboxylate at a high concentration shows this discoloration at an antibacterial agent stock solution silver concentration of 10 ppm or more. However, the antibacterial agent containing silver oxide shows no discoloration at this concentration. However, even when the antibacterial agent contains silver oxide, the antibacterial agent containing 200 ppm or more of silver concentration and containing no chelating agent is slightly white. Therefore, the present inventor has added a chelating agent to achieve high stabilization of silver, and has succeeded in obtaining a concentrated antibacterial agent that does not cause discoloration even when the silver concentration is 200 ppm or more. In particular, ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid (DTPA) is preferable as a chelating agent for stabilizing silver. Then, by dissolving silver oxide and phytic acid in an aqueous solvent to obtain an antibacterial agent containing a chelating agent, an antibacterial agent excellent in antiseptic and antifungal performance can be obtained.

Hereinafter, embodiments of the present invention will be specifically described.
Comparative Example 1
0.024 ml of 50% phytic acid solution was added to 999.976 ml of distilled water and stirred to completely dissolve 1.1 mg of silver oxide ground in a mortar (hereinafter referred to as antibacterial agent 1). The silver concentration of the prepared antibacterial agent 1 is about 1 ppm.

Example 1
0.024 ml of 50% phytic acid solution was added to 999.776 ml of distilled water and stirred, and 0.2 ml of DTPA was added to a solution in which 1.1 mg of silver oxide ground in a mortar was completely dissolved (hereinafter referred to as antibacterial agent 2). . The silver concentration of the adjusted antibacterial agent 2 is about 1 ppm.

Comparative Example 2
0.24 ml of 50% phytic acid solution was added to 999.76 ml of distilled water and stirred to completely dissolve 10.7 mg of silver oxide ground in a mortar (hereinafter referred to as antibacterial agent 3). The silver concentration of the adjusted antibacterial agent 3 is about 10 ppm.

Example 2
0.24 ml of 50% phytic acid solution was added to 997.76 ml of distilled water and stirred, and 2 ml of DTPA was added to a solution in which 10.7 mg of silver oxide ground in a mortar was completely dissolved (hereinafter referred to as antibacterial agent 4). The silver concentration of the prepared antibacterial agent 4 is about 10 ppm.

Comparative Example 3
2.4 ml of 50% phytic acid solution was added to 997.6 ml of distilled water and stirred to completely dissolve 107.4 mg of silver oxide ground in a mortar (hereinafter referred to as antibacterial agent 5). The silver concentration of the adjusted antibacterial agent 5 is about 100 ppm.

Example 3
After adding 2.4 ml of 50% phytic acid solution to 977.6 ml of distilled water, 20 ml of DTPA was added to a solution in which 107.4 mg of silver oxide ground in a mortar was completely dissolved (hereinafter referred to as antibacterial agent 6). The silver concentration of the prepared antibacterial agent 6 is about 100 ppm.

Comparative Example 4
6 ml of 50% phytic acid solution was added to 994 ml of distilled water and stirred to completely dissolve 268.5 mg of silver oxide ground in a mortar (hereinafter referred to as antibacterial agent 7). The silver concentration of the prepared antibacterial agent 7 is about 250 ppm.

Example 4
6 ml of 50% phytic acid solution was added to 944 ml of distilled water and stirred, and 50 ml of DTPA was added to a solution in which 268.5 mg of silver oxide ground in a mortar was completely dissolved (hereinafter referred to as antibacterial agent 8). The silver concentration of the prepared antibacterial agent 8 is about 250 ppm.

Comparative Example 1
0.024 ml of 50% phytic acid solution was added to 999.976 ml of distilled water and stirred to completely dissolve 1.5 mg of silver acetate. 8 mg of sodium bicarbonate was dissolved in the resulting solution, and 24 mg of sodium polyacrylate was added. The silver concentration of the prepared solution is about 1 ppm (hereinafter referred to as antibacterial agent 9).

Comparative Example 2
0.24 ml of a 50% phytic acid solution was added to 999.76 ml of distilled water and stirred to completely dissolve 15.5 mg of silver acetate. 80 mg of sodium bicarbonate was dissolved in the resulting solution, and 240 mg of sodium polyacrylate was added. The silver concentration of the prepared solution is about 10 ppm (hereinafter referred to as antibacterial agent 10).

Comparative Example 3
2.4 ml of a 50% phytic acid solution was added to 997.6 ml of distilled water, followed by stirring to completely dissolve 154.8 mg of silver acetate. 0.8 g of sodium bicarbonate was dissolved in the resulting solution, and 2.4 g of sodium polyacrylate was added. The silver concentration of the prepared solution is about 100 ppm (hereinafter referred to as antibacterial agent 11).

Comparative Example 4
6 ml of 50% phytic acid solution was added to 994 ml of distilled water and stirred to completely dissolve 387.0 mg of silver acetate. 2 g of sodium bicarbonate was dissolved in the resulting solution, and 6 g of sodium polyacrylate was added. The silver concentration of the prepared solution is about 250 ppm (hereinafter referred to as antibacterial agent 12).

  Next, Table 1 shows the measured silver concentration of the antibacterial agents 1 to 12 (measured with an atomic absorption spectrophotometer manufactured by Shimadzu Corporation) and the color change after ultraviolet irradiation for 7 days. In addition, as for the color at the time of preparation of antibacterial agents 1-9, all were colorless and transparent. The antibacterial agents showing no discoloration from Table 1 were 1 to 9, but as described above, the antibacterial agent is usually added at a rate of about 0.05 to 1%. The antibacterial agent 8 is the most suitable for 5, 6 and 8.

次に、抗菌剤を植物抽出成分より製造された消臭剤と配合し、抗菌消臭剤を得た。銀濃度０．５ｐｐｍおよび１ｐｐｍ溶液を２５ｃｍ^２あたり０．２ｍｌ付着させたときの抗菌力をＪＩＳ Ｚ２８０１（フィルム密着法）で試験した。その試験結果を表２に示した。表２の抗菌力試験結果より銀濃度１ｐｐｍ以上配合することにより十分な抗菌性能を発揮することが分かった。

Next, an antibacterial agent was blended with a deodorant produced from plant extract ingredients to obtain an antibacterial deodorant. Antibacterial activity when 0.2 ml of a silver concentration 0.5 ppm and 1 ppm solution was deposited per 25 cm ² was tested according to JIS Z2801 (film adhesion method). The test results are shown in Table 2. From the antibacterial activity test results shown in Table 2, it was found that sufficient antibacterial performance was exhibited when the silver concentration was 1 ppm or more.

上記の消臭剤に抗菌剤５、６、１１をそれぞれ１％添加し、抗菌消臭剤１、２、３を得た（設計銀濃度約１ｐｐｍ）。得られた抗菌消臭剤１、２、３を７日間放置し、沈殿の確認および銀濃度測定（(株)島津製作所製 原子吸光分光光度計にて測定）を行なった。その結果を表３に示した。表３より、抗菌消臭剤１および３は消臭剤成分と銀が反応し、黒色沈殿として析出したため溶液の銀濃度が低下している。しかし、キレート剤を含有する抗菌消臭剤２は沈殿がなく、溶液の銀濃度も設計どおりの値を示した。

1% of antibacterial agents 5, 6, and 11 were added to the above deodorizer to obtain antibacterial deodorants 1, 2, and 3 (designed silver concentration of about 1 ppm). The obtained antibacterial deodorants 1, 2, and 3 were allowed to stand for 7 days, and confirmation of precipitation and silver concentration measurement (measured with an atomic absorption spectrophotometer manufactured by Shimadzu Corporation) were performed. The results are shown in Table 3. From Table 3, since antibacterial deodorant 1 and 3 reacted with the deodorant component and silver and deposited as black precipitation, the silver concentration of the solution is falling. However, the antibacterial deodorant 2 containing a chelating agent had no precipitation, and the silver concentration of the solution showed a value as designed.

抗菌剤８を実際に化粧品に配合した配合成分を表４に示した。抗菌剤８を無配合のものを化粧品１、０．２％配合配合したものを化粧品２、０．４％配合したものを化粧品３、０．８％配合したものを化粧品４と呼ぶ。それぞれの設計銀濃度は０ｐｐｍ、０．５ｐｐｍ、１．０ｐｐｍ、２．０ｐｐｍである。次に、化粧品１〜４を検体とし、防腐・防カビ試験を行なった。試験菌液は、1)標準細菌混合菌（大腸菌、緑膿菌、黄色ブドウ球菌）、2)排水混合菌（厨房排水濾液）、3)真菌混合菌（クロコウジカビ、カンジダ、アオカビ、オーレオバシディウム）を用いて行なった。検体２０ｇを３本の滅菌バイアル瓶にとり、試験菌液1)〜3)をそれぞれに１％量（０．２ｍｌ）接種する。1)、2)を接種した検体は３０℃、3)を接種した検体は２５℃で保存し、７、１４、２１日目に生菌数の測定を、細菌はＳＣＤＬＰ寒天培地混釈法に、真菌はＧＰＬＰ寒天培地混釈法によって行なった。防腐・防カビ試験結果を表５に示した。化粧品１（抗菌剤８無配合）は、何れの接種菌ともに高いレベルの生菌数が持続していることから、防腐・防カビ効力は不十分であるが、化粧品２〜４（抗菌剤８配合）は、良好な防腐・防カビ効力を示した。

Table 4 shows the ingredients of the antibacterial agent 8 actually blended in cosmetics. The antibacterial agent 8 blended with no antibacterial agent 8 is referred to as cosmetic 1, 0.2 percent blended with cosmetic 2, 0.4 percent blended with cosmetic 3, and 0.8 percent blended with cosmetics 4. The respective designed silver concentrations are 0 ppm, 0.5 ppm, 1.0 ppm, and 2.0 ppm. Next, antiseptic and antifungal tests were conducted using cosmetics 1 to 4 as specimens. The test bacterial solution is 1) standard bacteria mixed bacteria (E. coli, Pseudomonas aeruginosa, Staphylococcus aureus), 2) wastewater mixed bacteria (kitchen wastewater filtrate), 3) fungal mixed bacteria (black mold, candida, blue mold, aureobasidi Um). Take 20 g of the sample in three sterilized vials and inoculate 1% (0.2 ml) of each of the test bacterial solutions 1) to 3). Samples inoculated with 1) and 2) should be stored at 30 ° C. Samples inoculated with 3) should be stored at 25 ° C, and the number of viable bacteria should be measured on days 7, 14, and 21. Fungi were performed by the GPLP agar medium pour method. Table 5 shows the results of the antiseptic and antifungal test. Cosmetic product 1 (containing no antibacterial agent 8) has a high number of viable bacteria for both inoculums, and thus has antiseptic and antifungal effects, but cosmetics 2 to 4 (antibacterial agent 8) Formulation) showed good antiseptic and antifungal effects.

  The antibacterial agent of the present invention relates to an antibacterial agent that utilizes the antibacterial effect of silver ions and is used in cosmetics, quasi-drugs, pharmaceuticals, and other sundries.

Claims (2)

An antibacterial agent characterized by dissolving silver oxide and phytic acid in an aqueous solvent and containing a chelating agent. The antibacterial agent according to claim 1, wherein the chelating agent is at least one selected from ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid.