WO2001050864A1 - Agents antibacteriens d'imputrescibilisation et compositions antibacteriennes d'imputrescibilisation - Google Patents
Agents antibacteriens d'imputrescibilisation et compositions antibacteriennes d'imputrescibilisation Download PDFInfo
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- WO2001050864A1 WO2001050864A1 PCT/JP2001/000113 JP0100113W WO0150864A1 WO 2001050864 A1 WO2001050864 A1 WO 2001050864A1 JP 0100113 W JP0100113 W JP 0100113W WO 0150864 A1 WO0150864 A1 WO 0150864A1
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- Prior art keywords
- antibacterial
- zinc
- agent
- zinc oxide
- antifungal
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Definitions
- the present invention relates to an antibacterial antibacterial agent and a fungicidal and antifungal composition, and more particularly to an improvement of an inorganic antibacterial antifungal agent.
- antibacterial and fungicide agents are used in a very wide range of fields related to human clothing, food and shelter, and these are broadly classified into organic and inorganic.
- organic antibacterial and antifungal agents examples include paraben, triclosan, quaternary ammonium salt, chronorehexidine hydrochloride, thiabendazonole, ikinorebendazine, kibutane, phenolic chlorophenol, chlorothaloninole and the like.
- Inorganic antibacterial and antifungal agents mainly include silicates, phosphates, zeolites, synthetic minerals, etc., which have replaced or carried antibacterial metals, mainly silver, copper, and zinc.
- silicates phosphates, zeolites, synthetic minerals, etc.
- antibacterial metals mainly silver, copper, and zinc.
- silver, zinc-substituted zeolite, silver-supported apatite, and silver-supported silica gel have been put into practical use.
- titanium oxide photocatalyst that utilizes the energy of ultraviolet light contained in sunlight or fluorescent light for antibacterial action.
- These antibacterial and antifungal agents were able to prevent bacterial contamination and deterioration of each product by blending them into building materials, daily necessities, and cosmetics.
- organic antibacterial and fungicides such as parabens, which are generally used as preservatives, have problems in terms of safety to the human body, and are inferior in safety to inorganic antibacterial and fungicides.
- the substance is an organic substance, it generally has low stability over time, such as decomposition by heat and a decrease in effect due to a change in pH. For this reason, applications such as kneading in resins that require relatively high temperatures are greatly restricted, and problems such as difficulty in using there were.
- inorganic antibacterial and fungicides are relatively safe for the human body and are less susceptible to heat and chemicals. Antibacterial effect was low. Furthermore, silver, which is frequently used as a raw material of an inorganic antibacterial and antifungal agent, easily discolors and thus has the problem of changing the appearance color of the product, and has the disadvantage of being expensive.
- the titanium oxide photocatalyst has the disadvantage that the antibacterial and antifungal effect cannot be expected in places where light does not shine, and the antibacterial and antifungal effect is slow even when irradiated with light.
- the present invention has been made in view of the above-mentioned problems of the prior art, and has as its object the purpose of the present invention is to provide an inorganic antibacterial agent which is superior in terms of overall antibacterial protection, safety, stability, and economic efficiency.
- the purpose is to provide a protective agent.
- the present inventors have conducted intensive studies and made zinc oxide as a main component, and as a mixture thereof, one selected from lithium, sodium, potassium hydroxide, hydrogen carbonate, and carbonate. Or, by including two or more types of alkali metals, the antibacterial and antifungal effects of each material alone act synergistically to achieve a drastically high effect, and completed the present invention. It led to.
- the antibacterial and antifungal agent of the present invention contains zinc oxide as a main component and one or more alkali metal salts selected from hydroxides of lithium, sodium, and potassium, hydrogen carbonates, and carbonates. It is characterized by.
- the content of the metal salt is 0.5% to 75% of the whole antibacterial agent.
- the antibacterial and antifungal agent of the present invention it is preferable to use zinc acetate, zinc sulfate, and zinc chloride as a raw material for synthesizing a zinc oxide component.
- the aqueous solution containing zinc ion and the aqueous solution of zinc ion are mixed at room temperature and atmospheric pressure so that the pH of the two aqueous solutions is kept at 7 to 9 by dropping the two aqueous solutions. While adjusting, it is continuously supplied to the reaction tank to react and synthesize, and the product is separated by filtration. It is preferably obtained by washing with water, drying and firing.
- the pH of the 10 wt% aqueous dispersion is preferably 9 to 14.
- the antibacterial force-proofing composition of the present invention is characterized by having an antibacterial force-proofing effect by containing the antibacterial force-proofing agent.
- FIG. 1 is a flowchart illustrating an example of a method for synthesizing an antibacterial antibacterial agent according to the present invention
- FIG. 2 is an explanatory diagram for explaining a method for evaluating antibacterial antistatic agent performance.
- Fig. 3 is a graph showing the relationship between the force-proofing performance against blue-powered viscous and the pH when powder is dispersed in water to form a 10 wt% slurry.
- FIG. 4 is an explanatory diagram showing a test sample used as a sample in Comparative Experiment 4.
- An object of the present invention is to provide an antibacterial and antibacterial agent which is generally excellent in all aspects of antibacterial and antifungal properties, safety, stability and economy.
- the antibacterial antibiotic agent according to the present invention does not use expensive raw materials such as silver-zinc-substituted zeolite, it is cheaper than conventional inorganic antibacterial agents.
- antibacterial and antifungal effects can be expected in some places, and there is little change over time of the antibacterial agent alone or the composition containing the antibacterial agent, which has often been a problem with conventional antibacterial agents. have.
- conventional inorganic antibacterial and fungicides have low efficacy and are highly effective against yeasts and other fungi.
- Examples of the zinc salt used for the synthesis of zinc oxide which is the main component of the antibacterial protective agent of the present invention, include inorganic salts such as zinc sulfate, zinc nitrate, zinc phosphate, zinc halide, zinc formate, and zinc acetate.
- Organic such as zinc propionate, zinc lactate, zinc oxalate, zinc citrate Acid salts can be used but need to be dissolved in water.
- lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like can be used as a raw material of the alkaline aqueous solution.
- lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like can be used as a raw material of the alkaline aqueous solution.
- sodium carbonate or carbonated lime it is particularly preferable to use sodium carbonate or carbonated lime.
- FIG. 1 is a flowchart illustrating an example of a method for synthesizing an antibacterial and antifungal agent according to the present invention.
- zinc acetate is used as a raw material for synthesizing zinc oxide.
- an aqueous solution containing zinc ions and an aqueous alkali solution in which hydroxides of lithium, sodium, and potassium, hydrogen carbonate, and carbonate are dissolved are prepared.
- zinc acetate is used to prepare an aqueous solution containing zinc ions, and sodium carbonate is dissolved in ion-exchanged water to prepare an alkaline aqueous solution.
- aqueous solutions are supplied at normal temperature and normal pressure to a reaction tank containing ion-exchanged water while adjusting the amount so that the pH of the reaction solution is 7 to 9, and mixed and diffused.
- the product obtained in this way can be obtained by filtering off with a centrifugal separator, washing with water, drying and further baking.
- drying was performed at 80 ° C. for 15 hours in the drying step, and firing was performed at 300 ° C. in the firing step.
- a pulverization treatment or the like may be performed after drying.
- the method for producing the antibacterial antimicrobial agent according to the present invention is not limited to the above-described method.
- zinc oxide and one or more alkali metal salts selected from lithium, sodium, and potassium may be used. If it is a method to be contained, it can be applied.
- the method of synthesizing zinc oxide which is the main component of the antibacterial antimicrobial agent of the present invention, can be roughly classified into a wet method in which the compound is synthesized in an aqueous solution and a dry method in which no solution is directly interposed.
- the wet method is a method of obtaining zinc oxide by washing, filtering, drying and calcining a basic zinc carbonate generally synthesized by mixing an aqueous solution containing zinc ions and an aqueous alkali solution containing carbonate ions.
- zinc oxide is directly formed without passing through basic zinc carbonate. It can be synthesized, washed with water, filtered and dried to obtain zinc oxide.
- dry methods include a method of heating metallic zinc in air (French method) and a method of heating zinc unite (Frank Unite) with a reducing agent such as coal or coat (US method).
- a method for easily and efficiently obtaining the antibacterial antibacterial agent of the present invention is as follows.
- the purpose is to intentionally leave the alkali metal salt adsorbed on the fine particles of zinc oxide or basic zinc carbonate dispersed in the water. Even with such a method, an antibacterial agent in which zinc oxide and an alkali metal salt are uniformly mixed can be obtained.
- the powder is washed with a salt of aluminum metal.
- An alkali metal salt may be uniformly mixed into the zinc oxide powder aggregate by immersion in an aqueous solution containing the solution and drying.
- the composition ratio of zinc oxide, which is the main component, and the metal salt of Alkali metal is 0.5 to 75% by weight. It is preferable that this is done. If this ratio is less than 0.5%, the desired antibacterial and antifungal effect cannot be obtained, and if it exceeds 75%, the initial antibacterial performance is good, but the performance of the composition due to the high hygroscopicity and dissolution of the alkali metal salt is high. This is because there is concern about the effects on the human body due to deterioration and strong resistance of the antibacterial agent itself.
- the antibacterial antifungal agent of the present invention may be used in the form of a powder as it is. However, if necessary, the antibacterial antifungal agent may be combined with other components to form the antibacterial antifungal agent. is there.
- liquid components such as water, alcohol, and silicone oil, Resins such as polyethylene, polypropylene, polyester, polyvinyl chloride, polycarbonate, nylon, epoxy resin, and acrylic resin; inorganic powders such as titanium oxide, silica gel, zeolite, apatite, dinoreconium phosphate, potassium silicate, and glass
- Resins such as polyethylene, polypropylene, polyester, polyvinyl chloride, polycarbonate, nylon, epoxy resin, and acrylic resin
- inorganic powders such as titanium oxide, silica gel, zeolite, apatite, dinoreconium phosphate, potassium silicate, and glass
- the body and the like can be blended as needed, but are not limited to these components.
- the use of the present invention is diverse, and industrial materials such as synthetic resin compositions, rubber, fibers, paper, paints, wood, etc., skin external agents, cosmetics, and toiletries, which have been conventionally concerned with contamination by bacteria and power plants.
- An excellent antibacterial and antibacterial property can be imparted by uniformly dispersing a certain amount in one composition or the like.
- the powders obtained here are referred to as Examples 11 to 1 to 18 by the numbers attached to the heads of the names of the added metal salts and are distinguished from each other. .
- the antibacterial and antifungal agent of the present invention contains zinc oxide and, as a mixture, one or more alkali metal salts selected from hydroxides of lithium, sodium, and potassium, hydrogen carbonates, and carbonates. It is characterized by the following. Therefore, the above-mentioned salt is added to zinc oxide.
- the following comparative examples were manufactured to examine the extent to which the antimicrobial protection effect was exhibited when an external salt was added or when zinc oxide was used alone.
- Example 1 Lithium in Example 1, sodium hydroxide and potassium, bicarbonate, instead of carbonate, 1. 0 g of carbonate Anmoniumu (NH 4) 2 C 0 3 dissolved in ion-exchanged water 2 O m 1 9. Og of commercially available zinc oxide powder (manufactured by Shodo Chemical Co., Ltd.) was added to the aqueous solution. This was sufficiently stirred and mixed with a homomixer, and dried at 110 ° C. for 14 hours using an oven to obtain an intended product.
- Example 1 The same operation as in Example 1 was carried out except that the lithium, sodium, and potassium hydroxides, bicarbonates, and carbonates added in Example 1 were not added, to obtain an intended product (zinc oxide only).
- the powders obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were tableted into a disc having a diameter of 8 mm using a tableting machine for pharmaceutical preparations, and were pre-cultivated for cultivation of Penicillium sp. , Aspergillus niger, Candida albicans ATCC10231, Pseudomonas aeruginosa ATCC 15442, Escherichia coli (Escherichia col i ATCC8739), Staphyhlococcus aureus FDA209P It was left still on the culture medium.
- the medium thus prepared is cultured for 72 hours at 25 ° C for fungi such as fungi, black mold and Candida, and 48 hours at 30 ° C for bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus. Then, the size of the produced growth inhibition zone was measured, and the antibacterial and antifungal performance was evaluated.
- fungi such as fungi, black mold and Candida
- 48 hours at 30 ° C for bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus.
- the evaluation of the antibacterial protection performance was performed according to the following criteria.
- FIG. 2 is an explanatory diagram for explaining a method for evaluating the antibacterial defense performance.
- a culture medium 4 is prepared in a petri dish 2, and the test strains of the fungi and bacteria described above have already been applied on the culture medium 4.
- a tablet 6 is placed at the center of the culture medium 4 and after a predetermined time, the growth inhibition zone 8 formed around the sample on the culture medium is inhibited by the size of the growth inhibition zone 8. Performance shall be evaluated. Sa It can be determined that the larger the growth inhibition zone, which is the distance from the sample to the periphery of the growth inhibition circle, the better the antibacterial performance.
- Table 1 shows the evaluation criteria.
- Examples 1 to 1 to 8 had higher antibacterial and antifungal properties than Comparative Examples 1 and 2.
- zinc oxide was originally known as an inorganic antibacterial substance.However, zinc oxide alone did not provide sufficient antibacterial and antibacterial properties. As a result, it was found that the antibacterial protection effect was improved. Since zinc oxide to which ammonium carbonate is added does not exhibit sufficient antibacterial properties, one or two selected from the group consisting of lithium, sodium, potassium hydroxide, hydrogencarbonate, and carbonate are used as a mixture. It was found that the antibacterial properties can be improved by containing the above alkali metal salts.
- the reaction was carried out while controlling the pH of the two aqueous solutions dropwise while maintaining the pH at a constant value during the reaction while stirring at normal pressure and normal temperature.
- the dripping time was about 20 minutes.
- the obtained precipitate was washed with water and centrifuged 5 times each, dried in an oven at 80 ° (:, 15 hours), pulverized by a personal mill, and calcined at 300 ° C for 1 hour. After pulverization, the desired product was obtained by passing through a 100-mesh sieve.
- Example 2 The same procedure as in Example 2 was repeated, except that 15.0 g of zinc sulfate heptahydrate was used instead of 87.8 g of zinc sulfate dihydrate in Example 2. I got
- Example 2 The desired product was obtained in the same manner as in Example 2, except that 54.5 g of zinc chloride was used instead of 87.8 g of zinc acetate dihydrate in Example 2.
- the powders obtained in Examples 2 to 4 were tablet-formed into a disk having a diameter of 8 mm using a tableting machine for pharmaceutical preparations, and the same antibacterial and antibacterial effect as in Comparative Experiment 1 was evaluated.
- Comparative Example 3 Zeomic TM (manufactured by Sinanen Zeomic Co., Ltd.), which is known to have a broad antibacterial spectrum with inorganic antibacterial agents, was commercialized as Comparative Example 4.
- Zinc flower (manufactured by Shodo Kagaku Co., Ltd.), which is most commonly used in cosmetics, was tableted into a disc shape with a diameter of 8 mm and tested under the same conditions as above.
- the powders of Examples 2 to 4 had antibacterial and antibacterial properties against each test bacterium, and the powder of Example 2 was particularly excellent in performance.
- the powders obtained in Examples 2 to 4 were analyzed by X-ray fluorescence, X-ray diffraction and infrared absorption spectroscopy. As a result, 5 to 10% by weight of sodium carbonate containing zinc oxide as a main component was present. I understand. For this reason, it is preferable to use zinc acetate, zinc sulfate, and zinc chloride as a raw material for synthesizing zinc oxide, and it is particularly preferable to use zinc acetate.
- the antibacterial and antifungal agent of the present invention had an excellent effect on fungi such as genius, black mold, and Candida fungus as compared with currently available inorganic antibacterial agents.
- Example 2 “87.8 g of zinc acetate dihydrate was dissolved in 30 Om1 of ion-exchanged water.
- Example 2 except that a solution prepared by dissolving 54.5 g of zinc chloride and 24.0 g of acetic acid in 30 Om1 ion-exchanged water was used instead of the ⁇ solution ''. The operation was performed to obtain the target.
- Table 4 below shows the evaluation results of the antibacterial protection performance.
- Example 6 ⁇ 14 and the powder obtained in Comparative Example 2 (only zinc oxide) used in Comparative Experiment 1 was tableted into a disk with a diameter of 8 mm using a tableting machine for pharmaceuticals. The performance of the antibacterial anti-biotic effect was evaluated.
- the antibacterial and antifungal performance was improved when the added amount of the mixed alkali metal salt was 0.5% or more, and the antibacterial and antifungal effect was improved as the mixing amount of the alkali metal salt was increased.
- 100% of sodium carbonate reduced the effect on fungi.
- the initial antibacterial performance is good when the mixing amount of the alkali metal salt exceeds 75%, the performance deterioration of the composition due to the high hygroscopicity and dissolution of the alkali metal salt and the strength of the antibacterial agent itself are high. There was concern about the effects of alkaline on the human body.
- the present inventors have made zinc oxide contain various metal salts, and studied whether there is any relationship between the physical properties and the antibacterial and antifungal effect.
- the pH of the slurry was 9 to 14 and showed high alkalinity.
- Fig. 3 shows the relationship between the anti-mildew performance against blue mold and the pH when powder is dispersed in water to form a 10 wt% slurry.
- the powder having a high force-proofing property exhibits high alkalinity when used as a slurry.
- the antibacterial and antifungal composition of the obtained antibacterial and antifungal composition containing the antibacterial and antifungal agent of the present invention was examined.
- the antibacterial antibiotic composition of the present invention is characterized by having an antibacterial antibiotic effect by containing the antibacterial antibiotic agent of the present invention as described above.
- the present invention will be described in more detail with reference to Examples of the antibacterial and antifungal composition of the present invention.
- the present invention is not limited to these embodiments.
- Example 2 Using the powder obtained in Example 2, an antibacterial paint was prepared based on the formulation shown in Table 7.
- Comparative Example 5 a paint in which the antibacterial protective agent of Example 2 was replaced with Zeomic TM (manufactured by Sinanen Zeomic Co.) was used. In Comparative Example 6, no antibacterial powder was added. A paint was prepared.
- the purpose of this is to measure the performance of an antibacterial agent immobilized on the tile surface, considering its application to a fungicide used in a bathroom.
- Figure 4 shows the test sample used as a sample.
- the mold used for the test was a wild strain of the genus Cladosporium, collected from the bathroom, and cultured, and the culture water containing the mold spores was sprayed on the sample surface.
- the tile joint sample was placed in a square petri dish and kept at 25 ° C, and the growth of the surface mold was visually observed approximately every week, and the growth of the mold was observed. Then, no mold growth was observed, slight mold growth was observed, slight mold growth was observed, and strong mold growth was marked XX.
- Table 8 shows the observation results of the sample surface.
- Example 7 has significant antifungal properties compared to other samples. all right.
- Zeomic TM manufactured by Sinanen Zeomic Co., Ltd.
- the paint turned brown and the design of the tile was significantly impaired. I got it.
- the antibacterial antibiotic agent of the present invention is also excellent in discoloration resistance.
- Silicone joint agent (Cemedine Co., Ltd. death!) Co - Nshi - run Bok Semeta "in 8060 White TM) 99. 0 g in the antibacterial Boryoku bi agent of Example 2 1. well was 0 g added to the batter (Example 8), 99. Og, the powder of Comparative Example 2 (Zeonic TM Co., Ltd., Sinenen Zeomic Co., Ltd.), 1. 1. g, and kneaded well (Comparative Example 7) and 99.5 g of a similar joint filler mixed with 0.5 g of TBZ (Thiabendazole TM, manufactured by Wako Pure Chemical Industries, Ltd.), an organic defense agent, and kneaded well. A test was conducted using Comparative Example 8.
- Each jointing agent was applied to a PET film in a 1.5 mm-thick plate and dried and fixed to prepare a sample.
- Each sample was cut into a 30mm X (horizontal) 3 Omm square and cut off.
- the fungus prevention test was performed according to the JISZ 291-11-1992 mold resistance test method and the method of general industrial products, and mixed with 5 kinds of pre-cultured mold spores and sprayed onto the sample The growth of the cells was visually observed under a microscope.
- Table 9 shows the observation results of the sample surface.
- the antibacterial antimicrobial agent of the present invention has at least the same performance as an existing antimicrobial agent when kneaded in the resin composition. Next, light stability was confirmed for the powder alone and the product system.
- the antibacterial antibiotic agent of the present invention has very good stability under any environment and does not cause discoloration.
- the powder of Comparative Example 3 was discolored by the aqueous sodium chloride solution.
- the discoloration of the fungicide reduces the usable chemicals.
- This sample was irradiated xenon lamp (illuminance approximately 285W / m 2) 3 0 hours (cumulative dose: about 30M J / m 2), and observing the color change of the sample surface by visual observation.
- the color difference of the sample surface before and after the measurement was measured using a spectrophotometer CM-1000 TM manufactured by Minolta Camera Co., Ltd. to determine the stability. Generally, it is said that if the color difference is 3 or more, the difference in color tone can be visually recognized.
- Table 11 Table 11 below. In the evaluation method by visual observation, “ ⁇ ” indicates that little yellowing is observed, “ ⁇ ” indicates that slight yellowing is observed, and “X” indicates that yellowing is clearly observed.
- Comparative Examples 7 and 8 were discolored enough to be clearly discriminated by visual observation. Since the color of Comparative Example 9 containing no antibacterial protective agent was not changed, it was found that the discoloration was caused by the mixed antibacterial protective agent.
- Example 8 in which the antibacterial antifungal agent of the present invention was mixed, almost no discoloration occurred in Comparative Example 9 in which nothing was mixed. It can be seen that no discoloration has occurred.
- the antibacterial antibacterial agent of the present invention has superior light stability as compared with Comparative Examples 7 and 8 of the conventional antibacterial antiviral agent.
- the antibacterial and antifungal agent of the present invention has an effect, stability, and antibacterial and antifungal activity against fungi such as lactobacillus, black mold, and Candida which were relatively poor at inorganic antibacterial agents currently on the market. Excellent effect persistence and little discoloration over time.
- the antibacterial antibiotic agent of the present invention by mixing the antibacterial antibiotic agent of the present invention, various synthetic resin compositions, industrial materials such as rubber, fiber, paper, paint, wood, and the like, compositions for external skin agents, cosmetics, toiletries, etc. Since the antibacterial and antifungal properties of the present invention can be imparted to the antibacterial and antifungal compositions of the present invention, the inorganic antibacterial agent is relatively weak at fungi, black mold, and Candida fungi. Excellent antibacterial and antifungal effect, with time Less discoloration.
- the antibacterial antibacterial agent of the present invention can provide an antibacterial agent having a high antibacterial antibacterial effect and a high sustainability efficiently and at low cost by a relatively simple method.
- the antibacterial / mildew-proof composition of the present invention can provide various compositions which are excellent in persistence of the antibacterial / mildew-proof mold and have little discoloration over time by mixing the antibacterial / mildew-proof composition of the present invention. it can.
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Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01900688A EP1161869B1 (en) | 2000-01-14 | 2001-01-12 | Antibacterial and mildew-proofing agents and antibacterial and mildew-proofing compositions |
DE60111685T DE60111685T2 (de) | 2000-01-14 | 2001-01-12 | Antibakterielle und schimmelverhindernde substanzen und antibakterielle und schimmelverhindernde zusammensetzungen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2000006889A JP4558122B2 (ja) | 2000-01-14 | 2000-01-14 | 抗菌防カビ剤及び抗菌防カビ組成物 |
JP2000/6889 | 2000-01-14 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US09/936,288 A-371-Of-International US20030044471A1 (en) | 2000-01-14 | 2001-01-12 | Antibacterial and mildew-proofing agents and antibactieral and mildew-proofing compositions |
US10/254,511 Continuation US20030138497A1 (en) | 2000-01-14 | 2002-09-26 | Inorganic antibacterial/antifungal agents |
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WO2001050864A1 true WO2001050864A1 (fr) | 2001-07-19 |
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PCT/JP2001/000113 WO2001050864A1 (fr) | 2000-01-14 | 2001-01-12 | Agents antibacteriens d'imputrescibilisation et compositions antibacteriennes d'imputrescibilisation |
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US (2) | US20030044471A1 (ja) |
EP (1) | EP1161869B1 (ja) |
JP (1) | JP4558122B2 (ja) |
DE (1) | DE60111685T2 (ja) |
WO (1) | WO2001050864A1 (ja) |
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US7674785B2 (en) * | 2000-06-22 | 2010-03-09 | The Procter & Gamble Company | Topical anti-microbial compositions |
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MXPA04009515A (es) * | 2002-04-22 | 2005-07-26 | Procter & Gamble | Uso de materiales con comportamiento de ionoforos de zinc. |
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- 2001-01-12 DE DE60111685T patent/DE60111685T2/de not_active Expired - Lifetime
- 2001-01-12 EP EP01900688A patent/EP1161869B1/en not_active Expired - Lifetime
- 2001-01-12 WO PCT/JP2001/000113 patent/WO2001050864A1/ja active IP Right Grant
- 2001-01-12 US US09/936,288 patent/US20030044471A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
DE60111685D1 (de) | 2005-08-04 |
US20030138497A1 (en) | 2003-07-24 |
EP1161869B1 (en) | 2005-06-29 |
JP2001199822A (ja) | 2001-07-24 |
EP1161869A1 (en) | 2001-12-12 |
EP1161869A4 (en) | 2002-05-29 |
US20030044471A1 (en) | 2003-03-06 |
JP4558122B2 (ja) | 2010-10-06 |
DE60111685T2 (de) | 2006-05-04 |
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