JP2017043597A - Silver-containing antibacterial agent stabilizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a stabilizing agent that specifically suppresses the decrease with time in antibacterial activity of silver-containing antibacterial agent such as silver ion carrier; an antibacterial composition containing the stabilizing agent; and a bath agent containing the antibacterial agent composition.SOLUTION: By using a stabilizing agent containing isopropyl methylphenol as an active ingredient, the decrease with time in antibacterial activity of a silver-containing antibacterial agent is specifically suppressed.SELECTED DRAWING: None

Description

  The present invention relates to a stabilizer for a silver-containing antibacterial agent, an antibacterial agent composition containing the stabilizer, and a bath agent containing the antibacterial agent composition.

In recent years, in the field of antibacterial technology, various studies have been conducted on inorganic antibacterial agents mainly composed of silver ions as antibacterial components because they are superior in safety, heat resistance and durability compared to organic antibacterial agents. . As a specific form of the antibacterial agent, it is possible to effectively exhibit the antibacterial performance of silver ions, and at the same time it is easy to use, so a structure in which silver ions are held in a porous ceramic is generally used. It has become. At that time, zeolite, layered silicate, calcium phosphate, zirconium phosphate, aluminum phosphate, soluble glass, titanium oxide and the like are used as the porous ceramic as the support.
In order to fully demonstrate the antibacterial performance of silver, it is more desirable to retain ionic silver that is rich in reactivity than to hold stable silver in the metallic state, and silver is immobilized on the support as silver ions. In addition, a technique for releasing silver as silver ions from a carrier is known.
However, as described above, a method of fixing silver ions to a carrier, a method of slowly releasing silver ions as a silver ion in a liquid to be treated, or a metal silver powder that has been conventionally used is directly administered into a liquid to be treated. The method has a problem that, under long-term storage, the antibacterial effect decreases as the silver ion elution amount decreases, and the preparation deteriorates.

On the other hand, in recent years, bathing agents have been added to bath water for the purpose of refreshing the mood of bathing by adding aroma and color to bath water, promoting blood circulation, activating metabolism and improving cooling and fatigue. However, the hot water with bathing agent is easy to grow because the ingredients contained in the bathing agent and the temperature of bath water (hot water) are suitable for breeding, and they smell of bath water. There is a problem in terms of hygiene in that it causes problems such as water and slime, and furthermore, maintaining a temperature suitable for re-boiled cold water and bathing for a long time.
Here, sterilization of household bath water has been conventionally performed by adding an appropriate amount of chlorine-based disinfectant, but although the disinfecting effect of chlorine-based disinfectant is excellent, depending on the input amount There were problems such as chlorine odor and skin irritation, and it was impossible to take a bath for a while after the injection, and it was necessary to control the input amount to an appropriate amount. In addition, a technique for dissolving silver ions in a bath agent has also been proposed, but silver chloride and silver iodide, which are generally known as silver ions, have low solubility in water and are dissolved in bath water together with the bath agent. It is difficult. Furthermore, silver chloride and silver iodide have a problem that chlorine ions and iodine ions are low in safety to the human body.

  Furthermore, an inorganic antibacterial agent having a structure in which silver ions are supported on a porous ceramic such as zeolite can effectively exhibit the antibacterial performance of silver ions, and is an easy-to-use form. It is also used as an antibacterial component in fields that require high safety such as cosmetics. However, when an antibacterial agent having this silver ion supported on a carrier is used as a bath agent, the antibacterial effect is deteriorated over time although it exhibits excellent antibacterial power in the initial stage. This is because silver ions react with other components such as chlorides, sulfur compounds, amino compounds and phenolic antioxidants contained in bathing agents, and chloride ions present in bath water, and have almost antibacterial properties. This is thought to be due to the fact that it becomes a salt or a complex ion that does not, or changes due to various chemical reactions caused by the influence of temperature, heat, or light. Furthermore, there also existed a problem that silver will discolor by these chemical reactions.

  In order to solve such problems, a bactericide that uses silver and an antibacterial metal other than silver (Patent Document 1), an amorphous synthetic aluminum silicate compound (Patent Document 2), silver-supported phosphoric acid A method using a zirconium-based (Patent Document 3) and silver hydroxycarboxylate (Patent Document 4) has been proposed.

JP-A-10-296272 JP 2000-063219 A JP 2000-007514 A JP 2010-037263 A

  The present invention relates to a stabilizer that specifically suppresses a decrease in antibacterial activity over time of a silver-containing antibacterial agent such as a silver ion carrier, an antibacterial agent composition containing the stabilizer, and the antibacterial agent An object of the present invention is to provide a bath containing the composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that isopropylmethylphenol specifically suppresses a decrease in antibacterial activity over time of a silver-containing antibacterial agent and completed the present invention. It came to do.

The gist of the present invention is specifically as follows.
1. A stabilizer for silver-containing antibacterial agents containing isopropylmethylphenol as an active ingredient.
2.1. The antibacterial agent composition containing the stabilizer and silver-containing antibacterial agent of description.
3. 1. The silver-containing antibacterial agent is a silver-supported zeolite. The antibacterial composition described in 1.
4.2. Or 3. A bath containing the antibacterial agent composition described in 1.

According to the present invention, by using isopropylmethylphenol, a decrease in antibacterial activity over time of the silver-containing antibacterial agent due to the influence of coexisting substances, temperature, heat, light, etc. is specifically suppressed, It is possible to provide an antibacterial agent composition capable of obtaining stable silver antibacterial activity.
In addition, by applying the antibacterial agent composition of the present invention to bath water, it is possible to suppress the growth of various bacteria that cause bath odor and slime, and the temperature is suitable for re-boiled cold water and bathing. Even if maintained for a long time, there is no concern about hygiene.
Furthermore, isopropylmethylphenol, which is an active ingredient of a stabilizer for silver-containing antibacterial agents, is a compound with high safety and particularly low skin irritation. Therefore, the antibacterial agent composition of the present invention can be used as a bath agent. It is safe even if you do.

  Hereinafter, a stabilizer for a silver-containing antibacterial agent containing isopropylmethylphenol of the present invention as an active ingredient, an antibacterial agent composition containing the stabilizer and a silver-containing antibacterial agent, and a bath containing the antibacterial agent composition The agent will be described in detail.

The stabilizer for the silver-containing antibacterial agent of the present invention contains isopropylmethylphenol as an active ingredient. Among these, isopropylmethylphenol is preferably 4-isopropyl-3-methylphenol. For example, it is sold by Osaka Kasei Co., Ltd. under the trade name Biosol.
In addition, isopropylmethylphenol is a compound also called cymene-5-ol or p-thymol. It has bactericidal and antibacterial properties, acts on bacteria that easily grow on sebum, has high safety, and is particularly low. It is an irritating compound.
Although the compounding quantity of the stabilizer in this invention will not be specifically limited if the desired effect with respect to a silver containing antibacterial agent is exhibited, if the silver containing antibacterial agent to be used is 100 mass parts, it will be 1-50 mass as isopropylmethylphenol. It is preferable to mix | blend in the range of 5 parts, The range of 5-25 mass parts is more preferable, Furthermore, the range of 7-20 mass parts is especially preferable. Moreover, when using as a bath agent, the range of 0.05-0.15 mass% is preferable with respect to the whole quantity of a bath agent, and the range of 0.05-0.10 mass% is more preferable.

The silver-containing antibacterial agent of the present invention means, for example, silver in an arbitrary shape exhibiting antibacterial activity in an aqueous environment in which microorganisms are present. For example, metallic silver such as colloidal silver and nanosilver, aqueous Examples include a silver compound that provides silver ions in a medium, a silver complex, and a silver carrier in which silver or silver ions are immobilized on a carrier. Of these, the silver-containing antibacterial agent of the present invention is preferably a silver carrier, and the carrier is porous such as zeolite, layered silicate, calcium phosphate, zirconium phosphate, aluminum phosphate, soluble glass, and titanium oxide. Ceramic ones are included. Among these, a silver-supporting zeolite is preferable as the silver-containing antibacterial agent of the present invention, and is available from, for example, Sinanen Zeomic Co., Ltd. under the trade name Zeomic. The silver-carrying zeolite is not particularly limited as long as the desired effect on the silver-containing antibacterial agent is exhibited, but a silver-carrying amount in the range of 0.5 to 10.0% by mass may be used. For example, when used as a bath agent, it may be added in a range of 0.03 to 10.0% by mass, preferably in a range of 0.1 to 1.0% by mass, based on the total amount of the bath agent. What is necessary is just to add.
Moreover, when it is set as the bath preparation of an aerosol formulation and a foam formulation, what is necessary is just to add so that the density | concentration in a stock solution may be in the range of 0.03-10.0 mass%, Preferably it is 0.1-1.0. What is necessary is just to add in the range of the mass%.
These bathing agents may be used so that the concentration of the silver carrier in the bath water is 0.01 to 30 ppm, preferably 0.1 to 10 ppm, more preferably 0.2 to 3.0 ppm.

  In addition to the above-mentioned silver-containing antibacterial agent and isopropylmethylphenol, the bathing agent of the present invention contains, as necessary, various components known in the art (hereinafter also referred to as “optional components”). It can mix | blend a seed | species or 2 or more types in combination. Although the arbitrary component which can be mix | blended with the bath agent of this invention is illustrated below, it cannot be overemphasized that it is not limited to the component etc. which were described here.

<Inorganic salts>
Chlorides such as sodium chloride, potassium chloride, ammonium chloride, bicarbonates such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium sulfate, aluminum sulfate, iron sulfate, sodium thiosulfate, potassium thiosulfate, sodium hyposulfite Sulfate such as sodium nitrate, potassium nitrate, calcium nitrate, sodium phosphate (excluding trisodium phosphate), phosphate such as sodium polyphosphate, calcium hydrogen phosphate, sulfur, sodium sulfide, potassium sulfide, Sulfides such as iron sulfite, silicic anhydride, metasilicic acid, mica powder, silicon compounds such as neutral clay, hydroxides such as sodium hydroxide and calcium hydroxide, borax, boric acid, calcium oxide, bromide Potassium, potassium permanganate, artificial callus salt, mineral springs, mineral sand, hot spring flowers, etc.
<Organic acids>
Malic acid, citric acid, succinic acid, fumaric acid, tartaric acid, pyrrolidone carboxylic acid and the like.
<Oil components>
Nuka oil, olive oil, soybean oil, liquid paraffin, white petrolatum, stearyl alcohol, myristic acid, lauric acid, palmitic acid, monoglyceride, triglyceride, rice bran extract, rice germ oil, ceramide, silicone, etc.

<Polymer substances>
Carboxymethylcellulose, styrene polymer emulsion, dextrin, casein, egg yolk powder, nonfat dry milk, and rice bran.
<Medicinal ingredients>
Menthol, camphor, methyl salicylate, salicylic acid, sodium salicylate, benzoic acid and the like.
<Enzymes>
Trypsin, α-chymotrypsin, bromelain, papain, protease, proctase, seratiothiopeptidase, lysozyme, ficin and the like.

<Perfume and essential oils>
Peppermint, eucalyptus, lemon, verbena, citronella, kayapte, salvia, thyme, clove, rosemary, hyssop, jasmine, chamomile, neroli, mugwort, perilla, marjoram, laurel, juniper berry, nutmeg, ginger, onion, garlic, lavender, Bergamot, Clary Sage, Peppermint, Basil, Rose, Petit Glen, Cinnamon, Mace, Citral, Citronellal, Borneol, Linalool, Geraniol, Nerol, Rodinol, Orange, Artemidia, Camphor, Menthol, Cineol, Eugenol, Hydroxycitronellal, Sandalwood, Costas, Labdanum, Amber, Musk, α-Pinene, Limonene, Methyl salicylate, Sowjutsu, Sandalwood, Valerian, Mussels, koboku, senkyu, spruce, touki, shrimp, peonies, peonies, ugongs, sanshin, keihi, carrots, bukuryu, dokukatsu, shobu, gaiyou, matsubusa, peony, jujube, fennel, chimney, campi, oil, etc. Amyl nitrite, trimethylcyclohexanol, allyl sulfide, nonyl alcohol, decyl alcohol, phenylethyl alcohol, methyl carbonate, ethyl carbonate, phenylacetate, guaiacol, indole, cresol, thiophenol, p-dichlorobenzene, p-methylquinoline , Isoquinoline, pyridine, absins oil acetic acid, acetic acid ester and the like.

<Pigments>
Talc, bengara, yellow iron oxide, magnesium silicate, mica, titanium, calcium carbonate, magnesium carbonate, titanium dioxide, anhydrous silicic acid, zinc oxide, and these coated grains (granule).
<Whitening ingredients>
Vitamin E ferulic acid ester, vitamin C and its derivatives, ellagic acid, kojic acid, α-hydroxy acid, hyaluronic acid and the like.
<Dyes>
Blue No. 1, Blue No. 202, Red No. 106, Red No. 2, Yellow No. 5, Yellow No. 4, Green No. 3, Orange No. 205, Yellow No. 202 (1), Green No. 204, Green No. 201, Red No. 102 Legal dyes such as Blue No. 2 and Red No. 3 and natural dyes such as chlorophyll, riboflavin, annatto and anthocyanin.

<Sulfur>
Sulfur, sodium thiosulfate, calcium thiosulfate, potassium thiosulfate, calcium sulfide, calcium disulfide, potassium sulfide, sodium sulfide, ammonium sulfide, barium sulfide, zinc sulfide, tin sulfide, antimony sulfide, iron sulfide, carbon disulfide, sulfide Phosphorus etc.
<Sebum secretion promoting ingredients>
Branched fatty acid cholesteryl ester, γ-oryzanol, yokuinin or yokuinin extract.
<Vitamins>
Vitamin A, Vitamin B, Vitamin C, Vitamin D, Vitamin E, Vitamin F, Vitamin H, Pantothenic acid, nicotinic acid or its derivatives, Vitamin E nicotinate, inosit and the like.

<Seaweed extracts>
Anaaaosa, Mill, Usbaaonori, Hitegusa, Susiaoonori, Casanori, Green Algae Plants such as Heraiwata, Hanemomo, Nagarami, etc. Brown algae plants such as Honda walla, Umitorano, Marubaamanori, Asakusanori, Susabinori, Cyprinus, Hirakusa, Macausa, Triashi, Hanafnori, Owl, Nori, Tosekirinsai, Akagiginanso, Nigiri nori, Nigiri norii Extracts obtained from red algae plants, etc.
<Cool sensations>
Menthol derivatives such as menthol, camphor and thymol, monocyclic compounds, bicyclic alcohols, tricyclic alcohols, tricyclic amides and the like.

<Moisturizing ingredients>
Organic acid salts such as sodium lactate, disodium tartrate, sodium pyrrolidone carboxylate, disodium glutamate, polyhydric alcohols such as isoprene glycol, propylene glycol, 1,3-butylene glycol, glycerin, xylose, xylitol, sorbitol, polyethylene glycol Water-soluble polymers such as polyvinyl alcohol, sodium alginate and polyvinylpyrrolidone, mucopolysaccharides such as chondroitin sulfate and hyaluronic acid, collagen and derivatives thereof, protein, keratin, fibroin and hydrolysates thereof.

<Surfactant>
Dioleic acid polyethylene glycol, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc.
<Bactericides other than silver-containing antibacterial agents>
Triclosan, dichloroisocyanuric acid, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, chlorhexidine chloride, hinokitiol, phenol, glycyrrhizinate and its derivatives.
<Anti-fading agent>
Amino acids such as glycine, alanine and glutamic acid; salicylic acid and its salts.
<Others>
Glucose, sucrose, trehalose, phytocollage, isoflavone, glycyrrhetinate and its derivatives, paraoxybenzoate, vegetable or fruit extract (extract), purified water, ionic water, deep ocean water, etc.

  What is necessary is just to set the compounding quantity of the arbitrary component mentioned above suitably in the range which does not impair the effect of this invention.

The bathing agent of the present invention is preferably dissolved within 20 minutes in a solubility test in which 1 g of bathing agent is dissolved in 1000 g of ion-exchanged water at 20 ° C. Thereby, when the bath agent of this invention is thrown into bath water, it can be dissolved rapidly.
In addition, the dosage form of the bath preparation of the present invention is not particularly limited, and for example, liquid preparations such as powders, granules, fine granules, tablets, blocking agents, and the like, emulsions, gels, liquids and the like. It can be set as a formulation, an effervescent formulation, an aerosol formulation, a foam formulation, etc.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
First, the prescription example is shown about the bath agent of this invention. In Examples, unless otherwise specified, parts means parts by mass.

<Prescription example>
Silver aluminosilicate (silver-supported zeolite: trade name “Zeomic AK10N”: manufactured by Sinanen Zeomic Co., Ltd .: silver supported amount of 5.5% by mass) 0.65 part, isopropylmethylphenol 0.1 part, glycine 0.1 part, anhydrous A total of 100 parts of silicic acid, 1.0 part of perfume and dry sodium sulfate was added to obtain a bath preparation formulation example A.

  Next, a test example shows that a stabilizer for a silver-containing antibacterial agent containing isopropylmethylphenol of the present invention as an active ingredient maintains the antibacterial activity of the silver-containing antibacterial agent.

<Efficacy test 1>
(1) Test sample “Bath preparation formula B” in which only the content of isopropylmethylphenol in “Bath preparation formula A” is changed to 0.05 parts or 0.15 parts, and the total amount is adjusted with dry sodium sulfate. Alternatively, “Bath Agent Formulation Example C” was obtained in the same manner as “Bath Agent Formulation Example A”. Further, as a prescription example not containing isopropylmethylphenol, a “bath preparation prescription example X” was obtained in the same manner as the above “bath preparation prescription example A”.
Bathing agent formulation examples B, A, C, and X thus obtained were filled into bottles (made of high-density polyethylene / ethylene-vinyl alcohol copolymer resin) in an amount of 600 g, and a cap (made of polypropylene) was used at a high temperature bath of 50 ° C. The samples stored for 3 months were used as test samples 1 to 3 and comparative test samples.
(2) Test Method Each of the test samples 1 to 3 and the comparative test sample was dissolved in purified water at 40 ° C. at a rate of 0.2 g / L, and a solution eluted for 24 hours was used as a test solution. This test solution was separated by filtration through a 0.2 μm membrane filter, and the solution was acidified with nitric acid, and quantitative analysis of silver ions eluted using an atomic absorption photometer (Hitachi, Z-2310, Z-8200) was performed. The analysis results are shown in Table 1.
The theoretical value of the silver ion concentration when all the silver ions were eluted from the silver-supported zeolite used was 71.5 μg / L, and the initial formulation (three months at 50 ° C.) of 0.65% by mass of the silver-supported zeolite was used. The measured elution silver concentration (before storage) was 72.1 μg / L.

The measured value of the initial elution silver concentration of the test samples 1 to 3 and the comparative test sample was 72.1 μg / L, and the elution silver concentration after 24 hours of the comparative test sample of Table 1 was 25.6 μg / L. And, the elution silver concentration after 24 hours of test samples 1 to 5 was 54.4, 65.4, 34.0 μg / L. Compared to the fact that the elution silver concentration is reduced to about one-third of the elution silver concentration (before storage at 50 ° C. for 3 months), the elution silver can be specifically detected by using silver-supported zeolite and isopropylmethylphenol together. It was revealed that the concentration reduction can be greatly suppressed. In particular, it is clear that Test Sample 2 containing 0.10% by mass of isopropylmethylphenol is preferable as the blending amount of isopropylmethylphenol because the reduction of the elution silver concentration after 24 hours is suppressed to less than 10%. became.
The above test results indicate that the antibacterial activity of the silver-containing antibacterial agent is maintained by the stabilizer of the silver-containing antibacterial agent containing isopropylmethylphenol of the present invention as an active ingredient.

  The stabilizer of the silver-containing antibacterial agent of the present invention specifically suppresses the decrease in antibacterial activity over time of the silver-containing antibacterial agent due to the influence of coexisting substances, temperature, heat, light, etc. The antibacterial activity of silver is obtained and useful.

Claims (4)

  A stabilizer for silver-containing antibacterial agents containing isopropylmethylphenol as an active ingredient.   An antibacterial agent composition comprising the stabilizer according to claim 1 and a silver-containing antibacterial agent.   The antibacterial agent composition according to claim 2, wherein the silver-containing antibacterial agent is a silver-supported zeolite.   The bath agent containing the antibacterial agent composition of Claim 2 or 3.