JP3995052B1 - Phosphate-adsorbing external preparation having microbial growth inhibitory action, product containing the same, and method for producing the same - Google Patents

Abstract

[Problem] To provide an external preparation applied to animals (including humans) and products having high biological safety and having a microorganism growth inhibitory action that can be produced at low cost.
An external preparation comprising amorphous ferric hydroxide produced under conditions where ferrous hydroxide is present as an active ingredient.
[Selection figure] None

Description

  The present invention relates to a phosphate-adsorbing external preparation having a microbial growth inhibitory action. Specifically, the present invention relates to an external preparation that is applied to a human or animal body to suppress the growth of microorganisms, and an external preparation that is applied to an object to suppress the growth of microorganisms.

Conventionally, various microbial growth inhibitors (antibacterial agents) have been proposed to suppress the growth of harmful microorganisms. For example, in order to give a certain product a microbial growth inhibitory action, a coating composition containing a microbial growth inhibitor that exhibits antibacterial, antifungal, and algal control properties has been proposed. Here, examples of conventional organic microorganism growth inhibitors include thiophene compounds, isothiazoline compounds, organic iodine compounds, and antibiotics (Patent Document 1), and inorganic microorganism growth inhibitors. And a titanium oxide thin film (Non-Patent Document 1).
JP 2002-114946 A Light Clean Revolution Akira Fujishima et al.

  Here, when an organic microbial growth inhibitor is used to give a product a microbial growth inhibitory action, depending on the use mode of the product, there may be a situation in which a problem occurs in the safety of humans and animals. Specifically, when the product is in contact with humans or animals (for example, shoe insoles, sanitary products, odor control agents applied directly to the human body), or when the product is in the living environment of humans or animals. When it exists (for example, furniture). Therefore, a component having a microbial growth inhibitory action with high biological safety is required. However, since a general antibacterial agent is a mechanism that directly kills bacteria by sterilization, there is a concern about adverse effects on the living body when applied to human skin or the like. Furthermore, since organic microbial growth inhibitors generally have high synthesis and production costs, there is a problem that these high-cost components cannot be applied to inexpensive products. In addition, in the case of a conventional inorganic microorganism growth inhibitor, for example, in the case of a titanium oxide thin film, because it is a mechanism that decomposes microorganisms with a strong oxidizing power based on light energy, it is assumed to be applied to human skin etc. In the same manner as the organic microorganism growth inhibitor, there is a concern about adverse effects on the living body. In addition, in the case of the titanium oxide thin film, there is a problem that there is a limitation in use such that light energy is required or the reactivity with the support is large. Therefore, the present invention provides an inorganic topical preparation that can exhibit an excellent microbial growth inhibitory action without adversely affecting a living body such as a human, can be manufactured at a low cost, and has almost no restrictions on use. With the goal.

  First, the present inventors are not an antibacterial agent of a type that directly acts on a bacterium and kills the bacterium as in the conventional antibacterial agent, but indirectly by changing the bacterium to an environment in which the bacterium is difficult to grow. An antibacterial agent of a type that suppresses the growth of bacteria (specifically, a type that suppresses the growth of the bacteria by cutting off the nutrient source of the bacteria) was examined. As a result, it has also been found that certain iron compounds have a phosphorus adsorption action sufficient to suppress the growth of bacteria and have excellent biological safety, and the present inventions (1) to (26) are provided. It has been completed.

  This invention (1) is an external preparation characterized by containing the ferric hydroxide produced | generated on the conditions in which ferrous species exist.

  In the present invention (2), after the ferric hydroxide is added to the ferrous aqueous solution with an oxidizing agent in an amount less than the equivalent of ferrous iron, an alkali is added and the pH at the end of the reaction is 1.5-5. .5 (preferably 1.5 to 4.0, more preferably 2.0 to 3.5).

  According to the present invention (3), the ferric hydroxide has an oxidizing agent in a ferrous aqueous solution and a redox potential of +400 to 770 mV (preferably +500 to 730 mV, more preferably +600 to 700 mV). After the addition, alkali is added and the pH at the end of the reaction is adjusted to 1.5 to 5.5 (preferably 1.5 to 4.0, more preferably 2.0 to 3.5). It is the external preparation of the said invention (1) produced | generated.

  In the present invention (4), the ferric hydroxide is added to an aqueous ferrous solution in an amount less than the equivalent amount of ferrous iron to give an oxidation-reduction potential of +400 to 770 mV (preferably +500 to 730 mV, The pH at the end of the reaction is 1.5 to 5.5 (preferably 1.5 to 4.0, more preferably 2.0 to 3.5, preferably after adding +600 to 700 mV). It is the external preparation of the said invention (1) produced | generated by adjusting so that it may become.

  The present invention (5) is the external preparation according to any one of the inventions (2) to (4), wherein the oxidizing agent is hypochlorite.

  The present invention (6) is the external preparation according to any one of the inventions (1) to (5), wherein the ferric hydroxide is amorphous.

  The present invention (7) is the external preparation according to any one of the inventions (1) to (6), further comprising glycerin.

  The present invention (8) is the external preparation according to any one of the inventions (1) to (7), which is phosphate ion adsorptive.

  The present invention (9) is the external preparation according to any one of the inventions (1) to (8) having a microbial growth inhibitory action.

  The present invention (10) is the external preparation according to any one of the inventions (1) to (9) for application to the human or animal body.

  The present invention (11) is the external preparation according to any one of the inventions (1) to (9) for application to a product.

  This invention (12) is a product containing any one external preparation of said invention (1)-(11).

  The present invention (13) is the product of the invention (12), which is a human or animal hygiene product, a human or animal medical product, a pharmaceutical product, a quasi-drug, a cosmetic product or a daily product.

  The present invention (14) includes a diaper or diaper sheet, a sanitary product (napkin or tampon), a panty liner or panty sheet, an incontinence pad, a pet paper diaper, a pet sanitary product, a mask, a sweat pad, a breast milk pad, and a medical sheet. The product according to the invention (12) or (13), which is a foul odor preventing agent, a wound wound (acne) external preparation, a baby powder, an antibacterial spray, a shoe insole or a garbage deodorant.

  In the present invention (15), an oxidizing agent is added to a ferrous aqueous solution in an amount less than the equivalent of ferrous iron, and then an alkali is added to adjust the pH to 1.5 to 5.5 (preferably 1.5 to 4.0, More preferably, it is a method for producing an external preparation containing ferric hydroxide, comprising a step of adjusting to 2.0 to 3.5).

  In the present invention (16), an oxidizing agent is added to a ferrous aqueous solution so that the redox potential is +400 to 770 mV (preferably +500 to 730 mV, more preferably +600 to 700 mV), and then an alkali is added to adjust the pH to 1. The ferric hydroxide is characterized by including a step of adjusting to become 5.5 to 5.5 (preferably 1.5 to 4.0, more preferably 2.0 to 3.5). It is a manufacturing method of the external preparation to contain.

  In the present invention (17), an oxidizing agent is added to a ferrous aqueous solution in an amount less than the equivalent amount of ferrous iron, and the oxidation-reduction potential is +400 to 770 mV (preferably +500 to 730 mV, more preferably +600 to 700 mV). And then adding an alkali to adjust the pH to 1.5 to 5.5 (preferably 1.5 to 4.0, more preferably 2.0 to 3.5). And a method for producing an external preparation containing ferric hydroxide.

  The present invention (18) is the production method according to any one of the inventions (15) to (17), wherein the oxidizing agent is hypochlorite.

  The present invention (19) is the production method according to any one of the inventions (15) to (18), wherein the ferric hydroxide is amorphous.

  The present invention (20) is the production method of any one of the inventions (15) to (19), further comprising a step of adding glycerin.

  The present invention (21) is the production method according to any one of the inventions (15) to (20), further comprising a step of dehydration, freeze drying or spray drying.

  This invention (22) is the manufacturing method of the said invention (21) which implements the addition process of glycerol before the process of spin-drying | dehydration, freeze-drying, or spray-drying after the said pH adjustment process, or the said process. is there.

  The present invention (23) is the production method according to any one of the inventions (15) to (22), wherein the external preparation is phosphate ion adsorptive.

  The present invention (24) is the production method according to any one of the inventions (15) to (23), wherein the external preparation has a microbial growth inhibitory action.

  The present invention (25) is the production method according to any one of the inventions (15) to (24), wherein the external preparation is applied to a human or animal body.

  The present invention (26) is the production method according to any one of the inventions (15) to (24), wherein the external preparation is applied to a product.

  Here, each term in this specification is explained. “Ferrous species” refers to substances in which iron is present in a divalent state, such as ferrous ions and ferrous compounds (eg, ferrous hydroxide). The “ferrous iron aqueous solution” is not particularly limited as long as it is an aqueous solution containing ferrous ions, and may contain other substances. “External preparations” are not limited to “external preparations” in the narrow sense relating to pharmaceuticals, quasi drugs and cosmetics, but are applied to the surface and / or inside of products in addition to those applied to the human or animal body. It is a concept that includes things. The “oxidant” is not particularly limited, and examples thereof include hypochlorite, hydrogen peroxide, and calcium hydroperoxide, and hypochlorite is preferable. “Microorganism” is a concept including bacteria, sputum and the like. The term “antibacterial” as used in the present invention means “sterilization”, “sterilization”, “disinfection”, “antibacterial”, which is the result of suppressing the growth of bacteria on the surface of animals (including humans) and objects. , “Bacteriostatic”, “antifungal”, “antiseptic” and the like.

  The best mode of the present invention will be described below. The technical scope of the present invention is not limited to the best mode.

  This external preparation contains as an active ingredient amorphous ferric hydroxide produced under conditions where ferrous species (eg, ferrous hydroxide) are present. Here, the active ingredient is characterized by having a high phosphorus adsorption capacity (phosphate absorption capacity). Due to its nature, when applied to animals (including humans) and things as an external preparation, the amount of phosphorus, which is an essential nutrient component, is significantly reduced from the application target, and as a result, it exerts a microbial growth inhibitory action in the application target. It is a mechanism. In this way, this drug suppresses the growth of microorganisms by removing phosphorus, which is an essential nutrient for the biological activities of microorganisms, and tries to solve the above problems, so it adversely affects human skin and symptoms. Never give.

Here, the active ingredient exhibiting high phosphorus adsorption capacity is amorphous ferric hydroxide, but if ferric hydroxide is used, the effect is not achieved. For example, ferric hydroxide produced by adding caustic soda to a ferric solution or commercially available ferric hydroxide does not show such a high phosphorus adsorption capacity (see Examples). This ferric hydroxide is based on the Eh (redox potential) -pH diagram in the Fe ²⁺ -Fe (OH) ₃ system, and it remains in ferrous iron when iron ions exist as stable chemical species. Is produced under extremely unstable conditions such as existing as ferric iron while being under Eh-pH conditions. And is in an unstable and extremely high amorphous state. Therefore, the -Fe-O-Fe-O-Fe- bond is unstable and easy to break, and this ferric hydroxide breaks the bond while newly forming Fe-OH group and phosphate ion. It is presumed that a very high adsorptive power is exhibited.

  Here, although the chemical structure of ferric hydroxide is not certain, it is presumed that it is the following structure based on experimental results and the like (however, the ferric hydroxide of the present invention is in the estimated form) It is not limited at all). In other words, the ferric hydroxide essentially contains ferric iron, and the oxygen atom or hydroxyl group is six-coordinated to the iron atom, and the six-coordinate iron is linked through the oxygen atom. It is estimated that Then, it is presumed that a certain type of water molecule present around the iron atom destabilizes the bond as a result of affecting the bond between the iron atom and the oxygen atom. And it is thought that an iron atom couple | bonds with an anion (phosphate ion) as a result of the exchange of the hydroxyl group or the destabilized oxygen atom coordinated to the iron atom, and an anion (for example, phosphate ion). Under the assumption, a preferred form is that in which -Fe-O-Fe-O-Fe- (cluster) has an appropriate size due to the presence of an appropriate hydroxyl group.

Here, in one manufacturing process of this external preparation, as explained below, ferrous hydroxide and an oxidizing agent (for example, sodium hypochlorite) are reacted to change to ferric hydroxide. Yes. Here, the oxidation-reduction reaction formula is shown below. In the following formula, for easy understanding, ferric hydroxide is simplified and described as “Fe (OH) ₃ ”.

Formula 1

  Thus, 1 mol of hypochlorous acid reacts with 2 mol of ferrous iron (that is, 1 mol of hypochlorous acid is equivalent to 2 mol of ferrous iron). And, as explained below, in the production process, the amount of the oxidizing agent used is less than the equivalent of ferrous iron (for example, less than 1 mole of hypochlorous acid in the case of 2 moles of ferrous iron). By doing so, the state where ferrous iron is not completely oxidized to ferric iron is constructed.

  Here, “amorphous” or “extremely amorphous” means at least 1 in the range of 5 ° to 80 ° in terms of 2θ value in powder X-ray diffraction using Cu Kα ray as an X-ray source. It has two amorphous halo shapes, meaning that there are no obvious crystalline peaks. Note that a slight crystalline peak may be observed in the amorphous halo figure depending on the starting material at the time of production. In such a case, in powder X-ray diffraction using Cu Kα ray as an X-ray source. The crystallinity peak intensity observed in the range of 5 ° to 80 ° as a 2θ value may be 5% or less in terms of the ratio of the corresponding crystalline reference material to the crystallinity peak (% X-ray diffraction intensity / reference material). . As specific% X-ray diffraction intensity / reference substance, those given by the following formula based on ASTM (American Society for Testing and Materials) D3906 can be used. The number of crystalline peaks used for calculating the integrated reflection intensity is not particularly limited, but a range of 1 to 8 is preferable.

Formula 2

  Thus, although the active ingredient is ferric hydroxide, it is generated under the condition that ferrous species (for example, ferrous hydroxide) exist as described above. Containing. The content of the ferrous species (for example, ferrous hydroxide) is not particularly limited, but is usually 5% by weight or less with respect to the dry weight (furnace dry, 105 ° C., 2 hours), and preferably 0. It is 01 to 4 weight%, More preferably, it is 0.1 to 2 weight%. In addition, at the time of manufacture, ferrous species are inevitably contained as described above, but the components may be removed by washing.

  Further, the external preparation may contain crystalline ferric hydroxide as long as amorphous ferric hydroxide as an active ingredient is present. In this case, the amorphous component is preferably 30% or more, more preferably 50% or more, and further preferably 75% or more.

  It is preferable that the external preparation further contains glycerin. Ferric hydroxide can be dried or aging (long-term storage), depending on whether -Fe-O-Fe-O-Fe- OH groups bound to iron are dehydrated and clusters are enlarged. It may change to a stable state and the adsorption power may be reduced. Therefore, for example, by mixing glycerin with ferric hydroxide in a wet state, dehydration of OH groups is unlikely to occur even when dried, so that a reduction in adsorption power can be remarkably suppressed. Here, the content of glycerin is preferably 20% by weight or less based on the dry weight (furnace dry, 105 ° C., 2 h).

  Next, the manufacturing method of the external preparation which concerns on this best form is demonstrated. In the external preparation (Step 1A), an oxidizing agent (for example, a hypochlorite aqueous solution) is added to the ferrous aqueous solution below the equivalent of ferrous iron (preferably 0.3 to 0.95, more preferably 0.00). 4 to 0.8) or (step 1B) an oxidizing agent (for example, hypochlorite aqueous solution) is added to ferrous aqueous solution with a redox potential of +400 to 770 mV (preferably +500 to 730 mV). (Step 2) After adding alkali (preferably caustic alkali), pH 1.5-5.5 (preferably 1.5-4.0, More preferably, it is obtained by adjusting to 2.0 to 3.5). Here, the order of (Step 1A) or (Step 1B) and (Step 2) is important, and if reversed, an external preparation with high phosphorus adsorption ability cannot be obtained. Hereinafter, each condition will be described.

  First, the ferrous salt that can be used in the ferrous aqueous solution is not particularly limited as long as it is a water-soluble salt, and examples thereof include ferrous sulfate, ferrous chloride, and ferrous nitrate. Ferrous sulfate is preferred because of the simple filtration of the precipitate. Further, the ferrous ion concentration in the ferrous aqueous solution is preferably 0.05 to 2M.

  Next, the usable oxidizing agent is not particularly limited, but is preferably hypochlorite. Here, examples of hypochlorite include sodium hypochlorite and calcium hypochlorite, and sodium hypochlorite is particularly preferable. In addition, although the hypochlorite density | concentration in hypochlorite aqueous solution is not specifically limited, The thing of 5-10% marketed can be used.

  Here, in the case of adopting Step 1A, the amount of the oxidizing agent to be used is an amount that is less than the equivalent of ferrous iron in the ferrous aqueous solution. Here, the amount of the oxidizing agent is preferably 0.3 to 0.95 in terms of equivalent ratio with respect to the amount of ferrous iron, and more preferably 0.4 to 0.8.

  In the case of adopting Step 1B, an oxidizing agent (for example, hypochlorite aqueous solution) is added to the ferrous aqueous solution, and the oxidation-reduction potential is +400 to 770 mV (preferably +500 to 730 mV, more preferably +600 to 700 mV). At this time, it is preferable to drop an oxidizing agent solution (for example, a hypochlorite aqueous solution) while stirring.

  In addition, the process 1A and the process 1B are not necessarily mutually independent processes, and when the process 1A is performed, the case where the process 1B is performed as a result and vice versa are included.

  Next, after adding a predetermined amount of oxidizing agent in Step 1A or after confirming that the oxidation-reduction potential is within the above range in Step 1B, Step 2 of adding alkali is performed. Here, the alkali is not particularly limited, but is preferably a caustic alkali. Examples of the caustic alkali include caustic soda and caustic potassium, and caustic soda is preferable. In addition, the alkali concentration (preferably caustic concentration) is, for example, 0.5 to 5N. Then, an alkaline aqueous solution (preferably a caustic aqueous solution) is added to a solution to which a predetermined amount of an oxidizing agent has been added (step 1A) or a solution in which the oxidation-reduction potential is within the above range (step 1B), and pH 1 It adjusts so that it may become 0.5-5.5 (preferably 1.5-4.0, more preferably 2.0-3.5). By performing this operation, amorphous ferric hydroxide precipitates, and the external preparation can be obtained.

  The external preparation is preferably in a dry form for handling. Here, the drying method is preferably dehydration, freeze drying, or spray drying, and according to these methods, the dehydration from the Fe—OH bond at the time of drying is small, so that the phosphate adsorption power is kept high.

  Furthermore, when glycerin is mixed before drying, at the time of drying, or after drying, a decrease in phosphoric acid adsorption power can be suppressed to a minimum. Here, the addition amount of glycerin is 20% or less (preferably 3 to 7%) with respect to the dry weight (furnace dry, 105 ° C., 2 hours). The timing of mixing glycerin is not particularly limited, but is preferably after pH adjustment and before drying.

  Next, the use of this external preparation is demonstrated. This external preparation can be applied to any object that is required to suppress the growth of microorganisms such as bacteria and sputum, for example, animals (including humans) and objects. The application areas of the external preparation are mainly in the fields of industry, life and medicine. Specific application fields in the industrial field include, for example, a slime control agent for paper and pulp, a wood preservative field, a water treatment field, and a separation field. Specific fields of use in daily life include household appliances such as refrigerators, washing machines, water purifiers, humidifiers, vacuum cleaners and dust filters, toiletries, baths, toilets, etc. Examples include supplies, toiletries such as sanitary napkins and toothbrushes, and stationery such as pencils. Specific usage fields in the medical field include textile products such as lab coats and curtains in hospitals, medical equipment such as wallpaper, building materials, and plastics.

  Here, typical usage modes for direct application to humans and animals are pharmaceutical, quasi-drug or cosmetic usage modes. Specifically, for example, it is applied in a dosage form such as a solubilizing system such as lotion, an emulsifying system such as cream or emulsion, a dispersion system such as calamine lotion, an aerosol filled with a propellant. In this case, if necessary, a drug, humectant, ultraviolet absorber, thickener, solubilizer, detergent, emulsifier, fat, pigment, A fragrance, a resin, an alcohol or the like may be appropriately blended. And as a specific product example of the said use aspect, a human or animal pharmaceutical, a quasi-drug, or cosmetics can be mentioned. More specifically, acne external preparations, odor control agents, baby powders, and antibacterial sprays can be exemplified.

  Moreover, when applying to a thing, a human or animal sanitary article, a human or animal medical article, or a household article can be mentioned as the said article, for example. In this case, a typical application mode is that the external preparation is applied to the surface of the object, or the external preparation is applied to the inside of the object (for example, when the object is fibrous, the external agent is applied between the fibers. And when the product is in the form of a resin, the external preparation is dispersed in the resin). Specific examples of products in use include diapers or diaper sheets, sanitary products (napkins or tampons), panty liners or panty sheets, incontinence pads, pet paper diapers, pet sanitary products, masks, sweat pads, breast milk pads Examples thereof include medical sheets or insoles of shoes. In the above example, an external preparation is applied to the surface or inside of the product from the beginning. However, the present invention is not limited to this. For example, an antibacterial treatment such as an antibacterial spray or a garbage deodorant is performed. Products for applying antibacterial treatment to non-existing products can also be mentioned as specific examples of the external preparation.

Here, when applying the external preparation to animals (including humans) or products, depending on the use, etc., it is preferable that the applied amount is, for example, ²⁰ to 200 g per 1 m ² of the animal or product surface area. It is. For example, when this external preparation is used as a pharmaceutical product, quasi-drug or cosmetic product, it may be applied to the product as necessary and when applied to the product. This antibacterial film is formed by mixing the external preparation with raw materials (for example, resin, prepolymer, monomer) to produce a product, or by mixing with a polymer having various film forming properties. May be applied to the product.

Production of external preparation 6% sodium hypochlorite (active chlorine 5%) was added dropwise to 800 ml of 0.1M ferrous sulfate aqueous solution with stirring so that the redox potential was 650 mV (drop amount = 29.8 g; The equivalent ratio = 0.588) and left for 3 minutes with stirring. 1N sodium hydroxide was added to the solution until the pH was stabilized at 2.7 to obtain an external preparation according to this example. The pH at the end of the reaction was 2.7, and the redox potential was +584 mV.

Component Analysis (1) Quantitative Analysis by Fe Form Quantitative analysis was performed on T-Fe, M-Fe, Fe ²⁺ and Fe ³⁺ for the above external preparations (where “T” means total, “M” Means metal). For T-Fe, stannous chloride reduction-potassium dichromate titration method, for M-Fe, mercuric chloride dissolution-potassium dichromate titration method, and for Fe2 ⁺ , an inert gas-filled acid. It measured by melt | dissolution-potassium dichromate titration method, and calculated about Fe3 ⁺ by the calculation method [Fe3 ⁺ = T-Fe- (M-Fe + Fe2 ⁺ )]. Table 1 shows the results. No. 1 is a paste-form external preparation. 2 is a freeze-dried external preparation.

(2) Component phase identification apparatus by X-ray diffraction (XRD): RINT-2200 type tube manufactured by Rigaku Corporation: Cu
Voltage-current: 40kV-40mA
Scanning speed: 4 ° / min
Scanning range: 5 ° -80 ° (2θ)
An X-ray diffraction test was performed under the above measurement conditions. The X-ray diffraction measurement charts are shown in FIGS.

  From the analysis results, sample no. 1 and no. In both cases, repidocrocite (γ-FeOOH) was detected very weakly. Moreover, both samples were broad except for the diffraction peak obtained in the X-ray diffraction chart, and it was found that the degree of amorphousness was extremely high.

Phosphorus adsorption ability test Phosphorus absorption ability was measured by taking a dry weight of 0.5 g of the external preparation according to this example, adding 20 ml of an ammonium phosphate solution (5.9 gP / l) to the mixture, and allowing to stand for 24 hours with occasional shaking. . And this was filtered and the phosphorus concentration of the filtrate was measured and computed. For comparison, ferric hydroxide produced by rapidly stirring 1N NaOH in a 1M FeCl ₃ aqueous solution so as to have a pH of 7.5 to 8.0, or ferric hydroxide was produced by dehydration. With respect to hydrous iron oxide (commercially available product), the adsorption ability was tested in the same manner. The results are shown in Table 3.

Addition example of glycerin, etc. Glycerin, ethanol and skim milk were added to the external preparation with a water content of 70% produced according to the above method, and 5% by weight of the external preparation was added and freeze-dried. Table 4 shows the phosphorus adsorption capacity of the dried product.

Antibacterial confirmation test (1) Bacterial strain used: E.coli ATCC 25922 (E. coli-Gram-negative bacteria)
· S.aureus ATCC 25923 (Staphylococcus aureus - Gram-positive bacteria)
· P.aeruginosa ATCC27853 (Pseudomonas aeruginosa - gram-negative bacteria)
(2) Test method and results Mura Hinton medium capable of culturing various types of bacteria mixed with external preparations according to Examples {addition amount: external preparation (dry weight) 2.5 g / 100 ml} and A non-mixed one was prepared for comparison. Then, the above three strains were cultured as representatives of bacteria causing problems in clinical medicine under the same conditions as in Examples and Comparative Examples, and the antibacterial degree of the external preparation according to the examples was observed. The results are shown in the table. Here, the antibacterial property was judged by the number of bacterial colonies grown in each medium. The evaluation criteria are “++++” with a very large number of colonies, “+” with a small number of colonies, “++” between ++ and +, and “−” with no colonies. . As a result, it was confirmed that the external preparation according to the example has a growth inhibitory effect (static antibacterial property) in both gram positive and gram negative bacteria. In addition, the Gram positive bacterium mentioned above indicates a violet color by Gram staining, and the Gram negative bacterium indicates a red color by Gram staining.

Production of Acne External Preparation (Skin Lotion) 5.0% by mass of external preparation according to this example, 10.0% by mass of ethanol, 1.0% by mass of hydroxyethyl cellulose, 7.0% by mass of glycerin, sodium guaiazulene sulfonate 0 0.5% by mass and 76.5% by mass of purified water were mixed and homogenized to produce the title agent.
Acne Improvement Effect Test The title test was conducted on 30 men and women (15 people per group) who suffered from acne from 15 to 25 years old. The test method was to clean the face thoroughly with cosmetic soap, then apply the above-mentioned acne external preparation twice a day (morning and evening) on the acne, and then coat with moisturizing adhesive bandage to prevent drying. The appearance of acne was evaluated one month later. The evaluation criteria were performed in two stages: (A) the symptom was improved compared to before application, and (B) the symptom was unchanged or deteriorated compared to before application. As a result, (A) evaluation was 23 out of 30 persons, and (B) evaluation was 7 persons (of 7 persons, 4 were unchanged). Moreover, no adverse effects on the skin due to the application of this drug were confirmed.

Application to mat material An antibacterial layer was formed on a mat material made of thick nylon by spraying a mixture of external preparation and water according to this example (external preparation 1 mass%) at a rate of 150 g / m ² . . And in order to confirm an effect about the mat | matte material dried until the water | moisture content evaporated, the mold resistance test was done with the test method according to JISZ-29112000. For comparison, a similar test was performed on a mat material on which an antibacterial layer was not formed. The evaluation criteria are 0: no mold on the test sample, 1: mold on the test sample does not exceed 1/3, 2: mold on the test sample exceeds 1/3 . As a result, in the mat material not subjected to antibacterial treatment, a large amount of ringworm bacteria were generated (evaluation: 2), whereas in the mat material subjected to antibacterial treatment, occurrence of ringworm bacteria was not confirmed (evaluation: 0). From this, when this external preparation was applied to a mat material, it was confirmed that the athlete's foot can be prevented from infecting others even if the athlete's foot holder uses the mat. .

FIG. 1 is an X-ray diffraction measurement chart of FIG. FIG. 1 is an X-ray diffraction measurement chart of FIG. FIG. 2 is an X-ray diffraction measurement chart of FIG. FIG. 2 is an X-ray diffraction measurement chart of FIG.

Claims (41)

  After adding an oxidizing agent to an aqueous solution of ferrous salt in an amount less than 0.3 equivalents to less than equivalents of ferrous ions, an alkali is added to adjust the pH at the end of the reaction to 1.5 to 5.5. An antibacterial agent applied to the human or animal body, containing ferric hydroxide produced in this way.   It is produced by adding an oxidizing agent to a water-soluble ferrous salt aqueous solution so that the oxidation-reduction potential becomes +400 to 770 mV, and then adding alkali to adjust the pH to 1.5 to 5.5 at the end of the reaction. An antibacterial agent applied to human and animal bodies, containing ferric hydroxide.   An oxidizing agent is added to a water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions to make the oxidation-reduction potential +400 to 770 mV, and then an alkali is added so that the pH at the end of the reaction is 1. An antibacterial agent applied to the human or animal body, containing ferric hydroxide produced by adjusting to 5 to 5.5.   The antibacterial agent according to any one of claims 1 to 3, wherein the oxidizing agent is hypochlorite.   The antibacterial agent according to any one of claims 1 to 4, wherein the ferric hydroxide is amorphous.   The antibacterial agent according to any one of claims 1 to 5, further comprising glycerin.   The antibacterial agent according to any one of claims 1 to 6, which is phosphate ion adsorptive.   The antibacterial agent according to any one of claims 1 to 7, which has a microbial growth inhibitory action.   The antibacterial agent according to any one of claims 1 to 8, which is a human or animal hygiene product, a human or animal medical product, a pharmaceutical product, a quasi-drug, or a cosmetic product.   The antibacterial agent according to claim 9, which is a foul odor preventing agent, a wound wound external preparation or a baby powder.   Adding an oxidant to the water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions, and then adding an alkali to adjust the pH to 1.5 to 5.5. A method for producing an antibacterial agent applied to a human or animal body, characterized by containing ferric hydroxide.   It includes a step of adding an oxidizing agent to a water-soluble ferrous salt aqueous solution so that the redox potential is +400 to 770 mV, and then adding an alkali to adjust the pH to 1.5 to 5.5. A method for producing an antibacterial agent containing ferric hydroxide and applied to the human or animal body.   An oxidizing agent is added to a water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions to make the redox potential +400 to 770 mV, and then alkali is added to adjust the pH to 1.5 to 5.5. The manufacturing method of the antibacterial agent applied to the body of a human or an animal containing the ferric hydroxide characterized by including the process adjusted so that it may become.   The manufacturing method as described in any one of Claims 11-13 whose said oxidizing agent is a hypochlorite.   The manufacturing method according to any one of claims 11 to 14, wherein the ferric hydroxide is amorphous.   The manufacturing method according to any one of claims 11 to 15, further comprising a step of adding glycerin.   The production method according to any one of claims 11 to 16, further comprising a step of dehydration, freeze drying or spray drying.   The manufacturing method of Claim 17 which implements the addition process of glycerol before the process of spin-drying | dehydration, freeze-drying, or spray-drying at the time of the said process after the said pH adjustment process.   The manufacturing method according to any one of claims 11 to 18, wherein the antibacterial agent is phosphate ion adsorptive.   The method according to any one of claims 11 to 19, wherein the antibacterial agent has a microbial growth inhibitory action.   After adding an oxidizing agent to an aqueous solution of ferrous salt in an amount less than 0.3 equivalents to less than equivalents of ferrous ions, an alkali is added to adjust the pH at the end of the reaction to 1.5 to 5.5. The antibacterial agent applied to the surface and / or inside of an object containing ferric hydroxide produced in this way.   It is produced by adding an oxidizing agent to a water-soluble ferrous salt aqueous solution so that the oxidation-reduction potential becomes +400 to 770 mV, and then adding alkali to adjust the pH to 1.5 to 5.5 at the end of the reaction. An antibacterial agent applied to the surface and / or inside of an object, containing ferric hydroxide.   An oxidizing agent is added to a water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions to make the oxidation-reduction potential +400 to 770 mV, and then alkali is added so that the pH at the end of the reaction is 1. An antibacterial agent applied to the surface and / or the inside of an object containing ferric hydroxide produced by adjusting to 5 to 5.5.   The antibacterial agent according to any one of claims 21 to 23, wherein the oxidizing agent is hypochlorite.   The antibacterial agent according to any one of claims 21 to 24, wherein the ferric hydroxide is amorphous.   The antibacterial agent according to any one of claims 21 to 25, further comprising glycerin.   The antibacterial agent according to any one of claims 21 to 26, which is phosphate ion adsorptive.   The antibacterial agent according to any one of claims 21 to 27, which has a microbial growth inhibitory action.   A product to which the antibacterial agent according to any one of claims 21 to 28 is applied.   30. The product of claim 29, wherein the product is a human or animal hygiene product, a human or animal medical product, a pharmaceutical product, a quasi-drug, a cosmetic product or a daily product.   Diapers or diaper sheets, sanitary products (napkins or tampons), panty liners or panty sheets, incontinence pads, pet paper diapers, pet sanitary products, masks, sweat pads, breast milk pads, medical sheets, antibacterial sprays, insoles The product according to claim 30, which is a garbage deodorant.   Adding an oxidant to the water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions, and then adding an alkali to adjust the pH to 1.5 to 5.5. A method for producing an antibacterial agent applied to the surface and / or inside of an object containing ferric hydroxide.   It includes a step of adding an oxidizing agent to a water-soluble ferrous salt aqueous solution so that the redox potential is +400 to 770 mV, and then adding an alkali to adjust the pH to 1.5 to 5.5. The manufacturing method of the antibacterial agent applied to the surface and / or inside of a thing containing ferric hydroxide.   An oxidizing agent is added to a water-soluble ferrous salt aqueous solution in an amount less than 0.3 equivalents to less than equivalents of ferrous ions to make the oxidation-reduction potential +400 to 770 mV, and then an alkali is added to adjust the pH to 1.5 to 5.5. The manufacturing method of the antibacterial agent applied to the surface and / or inside of a thing containing ferric hydroxide characterized by including the process adjusted so that it may become.   The manufacturing method according to any one of claims 32 to 34, wherein the oxidizing agent is hypochlorite.   36. The method according to any one of claims 32 to 35, wherein the ferric hydroxide is amorphous.   The manufacturing method according to any one of claims 32 to 36, further comprising a step of adding glycerin.   The production method according to any one of claims 32 to 37, further comprising a step of dehydration, freeze drying, or spray drying.   The manufacturing method of Claim 38 which implements the addition process of glycerol before the process of spin-drying | dehydration, freeze-drying, or spray-drying at the time of the said process after the said pH adjustment process.   40. The production method according to any one of claims 32 to 39, wherein the antibacterial agent is phosphate ion adsorptive.   41. The production method according to any one of claims 32 to 40, wherein the antibacterial agent has a microbial growth inhibitory action.

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