WO2024181494A1 - 抗菌剤 - Google Patents

抗菌剤 Download PDF

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Publication number
WO2024181494A1
WO2024181494A1 PCT/JP2024/007262 JP2024007262W WO2024181494A1 WO 2024181494 A1 WO2024181494 A1 WO 2024181494A1 JP 2024007262 W JP2024007262 W JP 2024007262W WO 2024181494 A1 WO2024181494 A1 WO 2024181494A1
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Prior art keywords
alcohol
platinum group
porous silica
antibacterial
group element
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English (en)
French (fr)
Japanese (ja)
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訓士 関本
彩子 寺島
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to JP2025503967A priority Critical patent/JPWO2024181494A1/ja
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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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to an antibacterial method that involves allowing platinum group element-supported porous silica to coexist with alcohol and act on it.
  • an antibacterial effect of alcohol against microorganisms has long been known, and alcohol is used in a wide variety of forms as an antibacterial agent.
  • an alcohol evaporating agent also called an alcohol volatilizing agent, etc.
  • an antibacterial effect can be obtained by setting the alcohol concentration in the space to 0.3 Vol% or more (Non-Patent Document 1), and the amount of alcohol, etc. is adjusted so that this concentration is achieved or maintained.
  • porous silica carrying particles containing platinum group metals can be used as an antibacterial porous material and an antifungal porous material (Patent Document 1, Patent Document 2), and it has been confirmed that when each material was added to a bacterial liquid and stored, it exhibited high antibacterial and antifungal properties against Escherichia coli, Staphylococcus aureus, and Penicillium. It has also been confirmed that storing this antifungal porous material together with food inhibits the growth of mold in the food (Non-Patent Document 2).
  • the present invention aims to provide a new means for enhancing the antibacterial effect of alcohol in antibacterial treatment within a specified space, and for maintaining or enhancing the antibacterial effect even when the amount of alcohol is reduced.
  • the inventors conducted extensive research to solve the above problems and discovered that by allowing the platinum group element-supported porous silica and alcohol to coexist and act, a significantly higher antibacterial effect (synergistic effect) can be obtained than the effect expected from the antibacterial effects of the platinum group element-supported porous silica and alcohol, respectively (additive effect).
  • An antibacterial agent comprising porous silica carrying a platinum group element.
  • the antibacterial agent according to [1] wherein the volume of pores within the range of ⁇ 20% of Dmax of the pores of the platinum group element-supporting porous silica is 90% or less of the total pore volume.
  • [7] The antibacterial agent according to any one of [1] to [6], which is used in the presence of alcohol.
  • An antibacterial agent comprising a platinum group element-supported porous silica and an alcohol.
  • the antibacterial agent according to [10] comprising the alcohol in the form of an alcohol vaporizer.
  • the antibacterial agent according to [10] or [11] containing the alcohol in an amount that results in a gas phase concentration of 0.015 vol% or more.
  • An antibacterial device comprising a platinum group element-supported porous silica and an alcohol generating source.
  • An article comprising the antibacterial agent according to any one of [10] to [12] or the antibacterial device according to any one of [13] to [15].
  • the article of [16] which is a bag, a container, a filter, a refrigerator, a freezer, a container, an air conditioner, an air purifier, a vehicle, a vessel, or an aircraft.
  • An antibacterial method comprising causing a platinum group element-supported porous silica to coexist with an alcohol.
  • a method for preserving food comprising preserving the food in the presence of platinum group element-supporting porous silica and alcohol.
  • the method for preserving according to [21] wherein the alcohol is in the form of an alcohol evaporant or an alcohol source.
  • the antibacterial effect of alcohol in antibacterial treatment within a specified space, can be synergistically enhanced by its coexistence with platinum group element-supported porous silica, providing a new means for maintaining or enhancing the antibacterial effect even when the amount of alcohol is reduced.
  • 1 shows the configuration of the test area used to measure the antibacterial activity of platinum group element-supported porous silica and ethanol in the following examples: 1: pouch bag, 2: platinum-supported mesoporous silica package, 3: polystyrene petri dish containing qualitative filter paper, 4: test bacteria (agar medium), 5: spacer.
  • platinum group element-supported porous silica means porous silica in which platinum group elements are supported in the form of metals and/or compounds.
  • the platinum group elements may be held in the form of particles on the surface of the porous silica, or a part of the platinum group elements may penetrate into the pore walls of the porous silica. At least a part of the platinum group elements may be bonded to silicon atoms of the porous silica directly or via other elements, or may be present in a form bound to other elements or compounds.
  • “porous silica” may be referred to as “mesoporous silica", but these terms are used interchangeably.
  • Platinum group elements are elements located in groups 8 to 10 of the fifth and sixth periods of the periodic table. That is, platinum group elements include platinum, palladium, rhodium, iridium, ruthenium, and osmium.
  • the platinum group element supported by the platinum group element-supported porous silica may be one type or two or more types. Among these, it is preferable that the platinum group element supported by the porous silica is platinum element.
  • the platinum group element-supporting porous silica satisfies the following formula (1).
  • A/(A+B) ⁇ 100 ⁇ 5% Formula (1) A represents the number of platinum group elements supported on the porous silica in the hydroxide state, and B represents the number of platinum group elements supported on the porous silica in the metallic state.
  • Platinum group element-supported porous silica that satisfies formula (1) is likely to exhibit excellent antibacterial effects in the presence of alcohol.
  • the alcohol is oxidized on the platinum surface, and the hydroxyl groups successively activate carbon monoxide and oxygen. Therefore, it is believed that the oxidation reaction proceeds more favorably when the proportion of platinum group elements present in the hydroxide state in the platinum group element-supported porous silica is 5% or more.
  • the number of platinum elements supported on the porous silica in the metallic state and the number of platinum elements supported on the porous silica in the hydroxide state can be measured by a conventionally known elemental analysis method.
  • the number of platinum elements supported on the platinum group element-supported porous silica and the number of platinum elements supported on the porous silica in the hydroxide state are measured by analysis using X-ray photoelectron spectroscopy under the following conditions.
  • the platinum hydroxide content (atm%) is calculated from the area % of the obtained photoelectron spectrum intensity.
  • platinum group elements supported in a metallic state are sometimes referred to as platinum group metals
  • platinum group elements supported in a hydroxide state are sometimes referred to as platinum group element-containing hydroxides.
  • A/(A+B) ⁇ 100 is preferably 5% or more, more preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. From the viewpoint of ensuring sufficient platinum in the metallic state, it is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less.
  • the platinum group element-supported porous silica may support multiple types of platinum group elements. Furthermore, when a platinum group metal and a platinum group element-containing hydroxide are supported on the platinum group element-supported porous silica, the type of platinum group element supported in the metal state and the type of platinum group element supported in the hydroxide state may be the same or different. However, as described above, it is preferable that the platinum group element is elemental platinum, and in this case, it is particularly preferable that the platinum group elements A and B in formula (1) are elemental platinum and satisfy the above formula (1).
  • the proportion of platinum group elements in 100 parts by mass of platinum group element-supported porous silica is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, from the viewpoint of improving the contact efficiency with alcohol, while from the viewpoint of durability, it is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less.
  • the average particle size of the platinum group element-supported porous silica is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and particularly preferably 5 ⁇ m or more, while in order to maintain a certain degree of particle surface area, it is preferably 1,000 ⁇ m or less, more preferably 800 ⁇ m or less, and particularly preferably 600 ⁇ m or less.
  • the average particle size of the platinum group element-supported porous silica can be measured using a laser diffraction particle size distribution analyzer.
  • the pore volume of the platinum group element-supported porous silica is not particularly limited, but from the viewpoint of improving the contact efficiency with alcohol, it is preferably 0.3mL/g or more, more preferably 0.4mL/g or more, and particularly preferably 0.5mL/g or more, while from the viewpoint of ease of production, it is preferably 1.6mL/g or less, more preferably 1.5mL/g or less, and particularly preferably 1.3mL/g or less.
  • the specific surface area of the platinum group element-supported porous silica is not particularly limited, but it is preferably 200m 2 /g or more, while it is preferably 1000m 2 /g or less, more preferably 800m 2 /g or less, and particularly preferably 700m 2 /g or less.
  • the values of the pore volume and the specific surface area can be measured by the BET method using nitrogen gas adsorption and desorption.
  • the platinum group element-supported porous silica preferably has a modal diameter (Dmax) of less than 20 nm on a pore distribution curve calculated from an isothermal desorption curve measured by a nitrogen gas adsorption/desorption method using the BJH method described in E. P. Barrett, L. G. Joyner, P. H. Haklenda, J. Amer. Chem. Soc., vol. 73, 373 (1951), i.e., a plot of differential nitrogen gas adsorption ( ⁇ V/ ⁇ (logd); V is the nitrogen gas adsorption volume) against pore diameter d (nm).
  • Dmax modal diameter
  • the lower limit of the modal diameter (Dmax) is preferably 2.0 nm or more, more preferably 3.0 nm or more, and most preferably 3.5 nm or more.
  • the total volume of pores in the platinum group element-supported porous silica within ⁇ 20% of the above-mentioned most frequent diameter (Dmax) is preferably 40% or more, and more preferably 50% or more, of the total volume of all pores.
  • the total volume of pores within ⁇ 20% of the above-mentioned most frequent diameter (Dmax) is preferably 90% or less of the total pore volume. This means that the diameters of the pores in the platinum group element-supported porous silica are uniform, with the pores being around the most frequent diameter (Dmax).
  • the most frequent pore diameter (Dmax) of the platinum group element-supported porous silica is 2.0 nm or more, and the volume of pores within ⁇ 20% of Dmax is 90% or less of the total pore volume, which is thought to be advantageous for the diffusion of reactants and products.
  • the percentage of the pore volume within ⁇ 20% of Dmax is calculated from the pore distribution curve calculated by the BJH method described in E. P. Barrett, L. G. Joyner, P. H. Haklenda, J. Amer. Chem. Soc., vol.
  • the platinum group element-supported porous silica preferably has a differential pore volume ⁇ V/ ⁇ (log d) at the most frequent diameter (Dmax) calculated by the above BJH method of 2 to 20 mL/g, and particularly preferably 3 to 12 mL/g (in the above formula, d is the pore diameter (nm), and V is the nitrogen gas adsorption volume).
  • Dmax the most frequent diameter
  • the platinum group element-supported porous silica is amorphous in terms of its three-dimensional structure, i.e., that no crystalline structure is observed, and it is particularly preferable that it has a three-dimensional pore structure. This means that when the platinum group element-supported porous silica is analyzed by X-ray diffraction, substantially no crystalline peaks are observed. In addition, in this specification, amorphous porous silica is extremely superior in productivity compared to crystalline porous silica.
  • the method for producing the platinum group element-supported porous silica in the present invention is not particularly limited, but it is preferably obtained by reducing a mixture of a platinum group element raw material, such as a platinum-containing compound or an organic complex containing a platinum group element, and porous silica.
  • a platinum group element-supported porous silica can be obtained by preparing an aqueous solution containing a platinum group element raw material, impregnating the porous silica, drying, and then performing a reduction treatment.
  • Examples of compounds containing platinum group elements include hydrochlorides, nitrates, sulfates, etc. of platinum group elements.
  • the platinum group element-supported porous silica in the present invention usually supports a specific amount of platinum group element-containing hydroxide, but the amount of hydroxide can be adjusted by the amount of silanol groups inside the porous silica that supports the platinum group element. That is, if the amount of platinum group element-containing hydroxide supported in the resulting platinum group-supported porous silica is to be increased, porous silica with a large amount of internal silanol groups can be used. On the other hand, if the amount of platinum group element-containing hydroxide supported in the resulting platinum group-supported porous silica is to be decreased, porous silica with a small amount of internal silanol groups can be used.
  • the amount of silanol groups inside the porous silica can be adjusted by the synthesis conditions when producing the porous silica.
  • an organic raw material is used as a template, and after the condensation polymerization reaction, the organic raw material must be removed by firing at a high temperature of 400 to 800°C. Therefore, it is difficult to obtain a platinum group element-supported porous silica that satisfies formula (1), such as the platinum group element-supported porous silica according to this embodiment.
  • the BET specific surface area, pore volume, and particle size of the porous silica before the platinum group element is loaded there are no particular limitations on the BET specific surface area, pore volume, and particle size of the porous silica before the platinum group element is loaded, and these may be appropriately selected so as to obtain the desired platinum group element-loaded porous silica. Therefore, the preferred ranges for these are the same as those given above for the platinum group element-loaded porous silica.
  • silica hydrogel obtained by hydrolyzing an alkali silicate or silica hydrogel obtained by hydrolyzing a silicon alkoxide can be produced by applying a method of hydrothermal treatment without aging, and preferably, a method of hydrolyzing a silicon alkoxide can be used.
  • Silicon alkoxides include tri- or tetraalkoxysilanes having a lower alkyl group with 1 to 4 carbon atoms, such as trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, or oligomers thereof, with tetramethoxysilane, tetraethoxysilane, and oligomers thereof being preferred.
  • the above silicon alkoxides can be easily purified by distillation, making them suitable as raw materials for high-purity silica gel.
  • the total content of metal impurities in the silicon alkoxide is preferably 100 ppm or less, and more preferably 10 ppm or less.
  • the content of metal impurities can be measured using the same method as that for measuring impurities in porous silica.
  • the hydrolysis of silicon alkoxide is usually carried out using 2 to 20 moles, preferably 3 to 10 moles, and particularly preferably 4 to 8 moles of water per mole of silicon alkoxide.
  • Hydrolysis of silicon alkoxide produces silica hydrogel and alcohol.
  • This hydrolysis reaction is usually carried out at room temperature to about 100°C, but it can also be carried out at higher temperatures by maintaining the liquid phase under pressure.
  • the reaction time depends on the composition of the reaction liquid (type of silicon alkoxide and molar ratio with water) and the reaction temperature, and the time until gelation varies, so it is not generally specified.
  • the reaction time is usually the time when the breaking stress of the hydrogel does not exceed 6 MPa.
  • hydrolysis can be promoted by adding acids, alkalis, salts, etc. as catalysts to the reaction system. However, the use of such additives causes the generated hydrogel to mature, as described below, so it is preferable not to use them in the production of porous silica.
  • silicon alkoxide is hydrolyzed to produce silicate, which is then condensed, increasing the viscosity of the reaction solution and finally gelling to form silica hydrogel.
  • silicate is then condensed, increasing the viscosity of the reaction solution and finally gelling to form silica hydrogel.
  • the above-mentioned hydrothermal treatment of the silica hydrogel produced by hydrolysis immediately without substantial maturation means that the silica hydrogel is subjected to the next hydrothermal treatment while maintaining the soft state it has immediately after production. It is not preferable to add acids, alkalis, salts, etc. to the hydrolysis reaction system of silicon alkoxide, or to make the temperature of the hydrolysis reaction too strict, as these will accelerate the maturation of the hydrogel. In addition, it is preferable not to use more heat or time than necessary in the post-treatments following hydrolysis, such as washing with water, drying, and leaving.
  • the conditions for hydrothermal treatment may be that the water is either liquid or gaseous, and may be diluted with a solvent or other gas, but liquid water is preferably used.
  • liquid water is preferably used to the silica hydrogel, usually 0.1 to 10 times by weight, preferably 0.5 to 5 times by weight, and particularly preferably 1 to 3 times by weight, of water is added to form a slurry, and the treatment is usually carried out at a temperature of 40 to 250°C, preferably 50 to 200°C, for usually 0.1 to 100 hours, preferably 1 to 10 hours.
  • the water used for hydrothermal treatment may contain lower alcohols, methanol, ethanol, propanol, etc.
  • This hydrothermal treatment method is also applicable to materials in which porous silica is formed in the form of a film or layer on a substrate such as particles, substrate, or tube for the purpose of creating a membrane reactor, etc.
  • the pore diameter and pore volume of the resulting porous silica tend to increase as the temperature increases.
  • the specific surface area of the resulting porous silica tends to reach a maximum once and then gradually decrease with the treatment time.
  • the temperature and time of the hydrothermal treatment makes it easier to obtain the porous silica of the present invention. Conversely, for example, if the temperature of the hydrothermal treatment is too high, the pore diameter and pore volume of the porous silica will become too large, and the pore distribution will also become broader. Conversely, if the temperature of the hydrothermal treatment is too low, the resulting porous silica will tend to have a low degree of cross-linking and poor thermal stability.
  • the hydrothermal treatment When the hydrothermal treatment is carried out in ammonia water, the same effect can be obtained at a lower temperature than when it is carried out in pure water. Furthermore, when the hydrothermal treatment is carried out in ammonia water, the porous silica finally obtained generally becomes hydrophobic compared to when it is treated in pure water, but the hydrophobicity becomes particularly high when the hydrothermal treatment is carried out at a relatively high temperature, usually 30 to 250°C, preferably 40 to 200°C.
  • the ammonia concentration of the ammonia water here is preferably 0.001 to 10 vol%, and particularly preferably 0.005 to 5 vol%.
  • the hydrothermally treated silica hydrogel is usually dried at 40 to 200°C, preferably 60 to 120°C. There are no particular limitations on the drying method, and it can be either batch or continuous, and can be dried at normal pressure or reduced pressure. If carbon derived from the silicon alkoxide raw material is present as needed, it can be removed by baking, usually at 400 to 600°C. To control the surface condition, it may also be baked at a maximum temperature of 900°C. Furthermore, it may be crushed and classified as needed.
  • Porous silica having a crystalline structure tends to have poor thermal stability in water, and when silicon alkoxide is hydrolyzed in the presence of a template such as a surfactant used to form pores in the gel, the gel easily becomes one that contains a crystalline structure.
  • a template such as a surfactant used to form pores in the gel
  • alcohol refers to an organic compound having a hydroxyl group, and may be a monoalcohol, a diol, or a polyhydric alcohol.
  • the term “alcohol” in the present invention is preferably ethanol, which is generally used as a food or food additive, from the viewpoint of use in the vicinity of food.
  • the state of the alcohol used together with the platinum group element-supported porous silica may be gaseous or may be liquid or solid as long as it can generate gaseous alcohol.
  • a solid it is preferable to use an alcohol that sublimates.
  • an alcohol aqueous solution of usually 50 vol% or more, preferably 70 vol% or more, more preferably 90 vol% or more, and even more preferably 99 vol% or more can be used, and can be used in the form of mist, droplets, or impregnated in some medium.
  • Alcohol impregnated in some medium is described as an "alcohol evaporating agent" in the present invention, which is preferable from the viewpoint of gradually evaporating gaseous alcohol and imparting sustained release.
  • the medium for impregnating alcohol may be any medium capable of supporting liquid alcohol and gradually evaporating gaseous alcohol, and is not particularly limited, but examples thereof include porous silica, diatomaceous earth, pulp, paper, felt, nonwoven fabric, cellulose, absorbent cotton, gel, starch, cyclodextrin, vermiculite, activated carbon, etc., and porous silica is preferable, and among them, B-type silica is more preferable from the viewpoint of having a sufficient pore volume.
  • the alcohol may be released from an "alcohol source".
  • the term "alcohol generation source” refers to a mechanism for volatilizing, vaporizing, or spraying alcohol, and there are no structural limitations as long as the mechanism has the function.
  • an example of a mechanism for volatilizing alcohol is a mechanism for holding a carrier impregnated with alcohol.
  • An example of a mechanism for evaporating alcohol is a heating mechanism or an ultrasonic mechanism.
  • An example of a mechanism for spraying alcohol is a sprayer including an atomizer.
  • the "alcohol generation source" preferably does not include food or beverage that generates/contains alcohol in order to prevent the deterioration of the food or beverage itself.
  • antibacterial means at least suppressing or preventing the growth of bacteria.
  • bacteria include bacteria and fungi, such as Escherichia coli, yeast, fungi (mold), etc., but are not limited thereto.
  • the "antibacterial” effect in the present invention is an antibacterial effect brought about by the coexistence of platinum group element-supported porous silica and alcohol. Although the mechanism of action of this antibacterial effect is not clear, it is believed that the platinum group element in the platinum group element-supported porous silica oxidizes gaseous alcohol to generate radicals, and these radicals suppress or prevent the growth of bacteria.
  • peracetic acid and acetic acid are produced from ethanol via acetaldehyde. It is believed that peracetic acid, which has a strong antibacterial effect, is produced from acetaldehyde.
  • the present invention relates to an antibacterial agent comprising a platinum group element-supported porous silica, which is characterized in that the antibacterial agent is used in the coexistence of alcohol.
  • the "coexistence" of the platinum group element-supported porous silica and alcohol means that gaseous alcohol, or evaporated or sublimated alcohol, can reach the platinum group element-supported porous silica.
  • the coexistence of the platinum group element-supported porous silica and alcohol can be confirmed by collecting gas within 30 cm from the platinum group element-supported silica gel and analyzing it by gas chromatography or gas chromatography mass spectrometry.
  • Methods for making the platinum group element-supported porous silica and alcohol coexist include, but are not limited to, using any form of alcohol itself or generating alcohol by a chemical reaction.
  • the alcohol may be made to coexist when the platinum group element-supported porous silica is started to be used, and then newly added so that it does not coexist, or it may be added intermittently to make it coexist during the entire period in which the platinum group element-supported porous silica is used.
  • the alcohol may be released from the above-mentioned alcohol evaporating agent or alcohol generating source.
  • the alcohol can be used in any amount as long as the desired antibacterial effect can be achieved in the presence of the platinum group element-supported porous silica, and can be appropriately set depending on factors such as the type, amount, and form of the platinum group element-supported porous silica that coexists, the type and amount of the antibacterial target, and the size of the space containing it.
  • the alcohol can be coexisted in an amount such that the gaseous alcohol concentration in the space in which the antibacterial agent is used is usually 0.01 vol% or more (100 ppm or more), preferably 0.015 vol% or more (150 ppm or more), more preferably 0.03 vol% or more (300 ppm or more), and even more preferably 0.06 vol% or more (600 ppm or more).
  • the upper limit is not particularly limited, but for example, the alcohol can be coexisted in an amount such that the gaseous alcohol concentration in the space in which the antibacterial agent is used is usually less than 0.3 vol% (less than 3000 ppm), preferably 0.2 vol% or less (2000 ppm or less), and more preferably 0.1 vol% or less (1000 ppm or less).
  • the alcohol concentration is preferably high in order to ensure that the desired antibacterial effect is sufficiently achieved, and is preferably low in order to reduce the amount of alcohol, which is economical, and to reduce the smell of alcohol.
  • alcohol in the present invention, can be present in a quantity ratio (proportion) of usually 20 ⁇ L or more, preferably 45 ⁇ L or more, and more preferably 90 ⁇ L or more per 1 L of the volume of the space in which the antibacterial agent is used, and although there is no particular upper limit, for example, alcohol can be present in an amount of usually less than 3000 ⁇ L, preferably 1000 ⁇ L or less, and more preferably 500 ⁇ L or less.
  • a large amount of alcohol makes it easier to fully obtain the desired effect, but a small amount of alcohol is preferable in that it is economical and the alcohol odor is less noticeable.
  • alcohol in the present invention, can be present in a quantity ratio (proportion) of usually 20 ⁇ L or more, preferably 45 ⁇ L or more, and more preferably 90 ⁇ L or more per gram of platinum group element-supported porous silica contained in the antibacterial agent, and although there is no particular upper limit, for example, alcohol can be present in an amount of usually less than 3000 ⁇ L, preferably 1000 ⁇ L or less, and more preferably 500 ⁇ L or less.
  • a large amount of alcohol makes it easier to fully obtain the desired effect, but a small amount of alcohol is preferable in terms of being economical and making it difficult to detect an alcohol odor.
  • the platinum group element-supported porous silica can be included in any amount, and can be appropriately set depending on factors such as the type, amount, and form of the coexisting alcohol, the type and amount of the antibacterial target, and the size of the space containing it.
  • the platinum group element-supported porous silica can be used in an amount of usually 0.001 g or more, preferably 0.01 g or more, more preferably 0.05 g or more, even more preferably 0.1 g or more, and particularly preferably 1 g or more, and the upper limit is not particularly limited, but for example, it can be used in an amount of usually 10 g or less, preferably 5 g or less, more preferably 3 g or less, even more preferably 1 g or less, and particularly preferably 0.5 g or less.
  • a large amount of platinum group element-supported porous silica makes it easier to fully obtain the desired effect, but a small amount is more economical and preferable from the viewpoint of productivity.
  • the antibacterial agent of the present invention can have any form, for example (but is not limited to) powder, granules, pellets, tablets, etc., and if necessary, can be further formulated into a desired form by appropriately adding one or more of the other ingredients commonly used in the manufacture of antibacterial agents, such as (but not limited to) excipients, binders, lubricants, antioxidants, etc., in amounts that do not impair the effects of the present invention.
  • the antibacterial agent according to the present invention may be placed in a packaging material that allows the permeation of gaseous alcohol and does not release the platinum group element-supported porous silica, if necessary.
  • the packaging material may be cloth, paper, resin film, etc.
  • the present invention relates to an antibacterial agent comprising a platinum group element-supported porous silica and an alcohol.
  • the platinum group element-supported porous silica can be contained in any amount as long as the desired antibacterial effect can be achieved in the presence of alcohol, and the amount is the same as the range of amounts of platinum group element-supported porous silica listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the platinum group element-supported porous silica can be in any form, such as (but not limited to) powder, granules, pellets, tablets, etc., and if necessary, can be further formed into a desired form by appropriately adding one or more of the other ingredients, such as (but not limited to) excipients, binders, lubricants, antioxidants, etc., that are generally used in the manufacture of antibacterial agents, in amounts that do not impair the effects of the present invention.
  • the alcohol can be contained in any form, but from the viewpoints of productivity and ease of handling, the above-mentioned alcohol evaporative form is preferred.
  • alcohol in the antibacterial agent according to the present invention, can be included in any amount as long as the desired antibacterial effect can be achieved in the presence of the platinum group element-supported porous silica, and the amount is the same as the range of alcohol amounts listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the antibacterial agent according to the present invention is used under conditions in which the platinum group element-supported porous silica and alcohol coexist, and as long as this "coexistence" can be achieved during use of the present invention, the two may be packaged together or may be packaged separately.
  • the packaging can be made of a material that allows gaseous alcohol to pass through, and that does not release the platinum group element-supported porous silica and alcohol, and for example, cloth, paper, resin film, etc. can be used.
  • the antibacterial agent of the present invention includes platinum-loaded porous silica and an ethanol evaporating agent.
  • Antibacterial Device Comprising a Platinum Group Element-Supported Porous Silica and an Alcohol Generation Source
  • the present invention relates to an antibacterial device comprising a platinum group element-supported porous silica and an alcohol generation source.
  • the "alcohol generation source” may be one of those described above, and when the antibacterial device of the present invention is used in a food preservation method, it is preferable that the alcohol generation source is provided with a mechanism for volatilization or spraying in order to prevent deterioration of the food due to heating.
  • the "alcohol generation source” can contain any amount of alcohol as long as the desired antibacterial effect can be achieved in the presence of the platinum group element-supported porous silica, and the amount is the same as the range of alcohol amounts listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the antibacterial device according to the present invention may contain any amount of platinum group element-supported porous silica as long as the desired antibacterial effect can be achieved in the presence of alcohol, and the amount is the same as the range of amounts of platinum group element-supported porous silica listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the platinum group element-supported porous silica can be in any form, such as (but not limited to) powder, granules, pellets, tablets, etc., and if necessary, can be further formed into a desired form by appropriately adding one or more of the other ingredients, such as (but not limited to) excipients, binders, lubricants, antioxidants, etc., that are generally used in the manufacture of antibacterial agents, in amounts that do not impair the effects of the present invention.
  • the antibacterial device of the present invention is used under conditions in which the platinum group element-supported porous silica and alcohol coexist, and as long as this "coexistence" can be achieved during use of the present invention, the platinum group element-supported porous silica and the alcohol generating source may be integrated or separate.
  • the antibacterial device of the present invention includes a mechanism for holding the carrier impregnated with platinum-loaded porous silica and ethanol, or a mechanism for spraying ethanol.
  • the present invention relates to an article comprising the above-mentioned antibacterial agent comprising a platinum group element-supported porous silica and an alcohol, or an antibacterial device comprising a platinum group element-supported porous silica and an alcohol generating source.
  • the antibacterial agent and antibacterial device of the present invention can be used without restriction in any application that requires the suppression or prevention of bacterial growth, and can be equipped on various items that require the suppression or prevention of bacterial growth.
  • articles equipped with the antibacterial agent and antibacterial device according to the present invention include (but are not limited to) bags, containers, filters, refrigerators, freezers, containers, air conditioners, air purifiers, vehicles, ships, aircraft, etc., and in particular, items used for storing and transporting food are preferred.
  • the present invention also relates to an antibacterial method comprising the coexistence of a platinum group element-supported porous silica and an alcohol.
  • the method of "allowing the platinum group element-supported porous silica to coexist with alcohol” may be any method that allows for the "coexistence" described above in "4. Antibacterial agents used under conditions in which alcohol coexists," and may include, but is not limited to, any form of alcohol itself or a method in which alcohol is generated by a chemical reaction.
  • the alcohol may be allowed to coexist when the platinum group element-supported porous silica is first used, and then newly added thereafter so that it does not need to be allowed to coexist, or it may be added intermittently throughout the entire period in which the platinum group element-supported porous silica is used.
  • the platinum group element-supported porous silica can be used in any amount as long as the desired antibacterial effect can be achieved in the presence of alcohol, and the amount is the same as the range of amounts of platinum group element-supported porous silica listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the alcohol in the antibacterial method according to the present invention, can be used in any amount as long as the desired antibacterial effect can be achieved in the presence of the platinum group element-supported porous silica, and the amount is the same as the range of alcohol amounts listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the platinum group element-supported porous silica and the alcohol can have any form as long as the desired antibacterial effect can be achieved in the presence of both, and can, for example, have the form of the above-mentioned antibacterial agent, antibacterial device, and articles comprising them.
  • the antibacterial method of the present invention includes causing the platinum-loaded porous silica to coexist with ethanol, and the ethanol can be in the form of an ethanol evaporant, a mechanism for holding an ethanol-impregnated carrier, or a mechanism for spraying ethanol.
  • the present invention also relates to a food preservation method comprising preserving food in the coexistence of platinum group element-supported porous silica and alcohol.
  • "coexistence of platinum group element-supported porous silica and alcohol” may be any method that allows the "coexistence” described in "4.
  • Antibacterial agent used under conditions in which alcohol coexists" above and may be any method, including, but not limited to, using any form of alcohol itself or generating alcohol by a chemical reaction.
  • Alcohol may be made to coexist when the platinum group element-supported porous silica is first used, and then newly added thereafter so that it does not need to be made to coexist, or it may be added intermittently throughout the entire period in which the platinum group element-supported porous silica is used.
  • the platinum group element-supported porous silica can be used in any amount as long as the desired antibacterial effect can be achieved in the presence of alcohol, and the amount is the same as the range of amounts of platinum group element-supported porous silica listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • alcohol in the preservation method according to the present invention, can be used in any amount as long as the desired antibacterial effect can be achieved in the presence of the platinum group element-supported porous silica, and the amount is the same as the range of alcohol amounts listed above in "4. Antibacterial agents used in the presence of alcohol.”
  • the platinum group element-supported porous silica and the alcohol can have any form as long as the desired antibacterial effect can be achieved in the presence of both, and can, for example, have the form of the above-mentioned antibacterial agent, antibacterial device, and articles comprising them.
  • the preservation method of the present invention includes preserving food in the presence of platinum-loaded porous silica and ethanol, where the ethanol can be in the form of an ethanol evaporant, a mechanism for holding an ethanol-impregnated carrier, or a mechanism for spraying ethanol.
  • Antibacterial Activity Evaluation Test (1) Configuration of Test Groups The configuration of each test group used in the measurement of antibacterial activity is as shown in FIG. Four items were placed in a barrier nylon pouch bag (A92-W manufactured by Mitsubishi Gas Chemical Co., Inc.): platinum-supported mesoporous silica (powder) (packaged in a nonwoven bag), a polystyrene petri dish ( ⁇ 55 ⁇ 17 mm) containing qualitative filter paper (No. 1, ⁇ 47 mm), the test bacteria, and a spacer for ensuring an air space within the bag.
  • the platinum-supported mesoporous silica was produced by the following method.
  • the gel was then quickly taken out and crushed through a nylon net with a mesh size of 600 microns to obtain a powdered wet gel (silica hydrogel).
  • 450g of this hydrogel and 450g of pure water were charged into a 1L glass autoclave and hydrothermal treatment was carried out at 130°C for 3 hours.
  • the mixture was filtered through a 5A filter paper, and the filter cake was dried under reduced pressure at 100° C. without washing with water until a constant weight was obtained, thereby obtaining mesoporous silica.
  • the obtained mesoporous silica was treated so that the Pt content was 1%, thereby obtaining a powdered platinum-supported mesoporous silica.
  • the container for the agar medium was a ⁇ 55 x 17 mm polystyrene petri dish, and after the bacteria were seeded, the dish was left to stand in a pouch with the lid removed.
  • a certain amount of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent, purity 99.5% by mass or more) was dropped onto the qualitative filter paper, and the dish was placed in the pouch with the lid closed, allowing the gaseous ethanol to diffuse into the gas phase inside the pouch.
  • the volume of the sealed space in each test group was 1100 cm3 .
  • test fungi and culture conditions The test fungi and their culture conditions were as shown in Table 1. 50 ⁇ L of the previously cultured fungal liquid (for mold, conidial liquid obtained by suspending conidia in sterilized demineralized water, and for yeast and bacteria, fungal liquid obtained by liquid culture at 30° C. for 24 hours) was taken and smeared on the agar medium.
  • the antibacterial activity was evaluated by visual observation of the test bacteria after each test section was kept at a constant temperature under the above-mentioned culture conditions. After the constant temperature storage, the petri dishes containing the test bacteria were removed from the pouches, and the culture appearance of the test bacteria in the test section that did not contain platinum-loaded mesoporous silica and ethanol was compared and evaluated.
  • test areas in which conidial germination did not occur or stopped early were defined as having antibacterial activity (-), and test areas in which conidial germination and hyphae elongation occurred were defined as having no antibacterial activity (+).
  • test sections in which the same level of growth was observed as in test sections that did not contain the agent were defined as having no antibacterial activity (+), and test sections in which no growth was clearly observed compared to test sections that did not contain the agent were defined as having antibacterial activity (-).
  • Test result 1 The evaluation results of antibacterial activity against mold are shown in Table 2 below.
  • the amount of ethanol dropped onto qualitative filter paper was set to 0 ⁇ L or 200 ⁇ L
  • the amount of platinum-supported mesoporous silica added was set to 0 g or 0.5 g
  • the mixture was stored at a constant temperature for two types of mold. It was determined that antibacterial activity was present only in the test group (Example 1) containing both ethanol and platinum-supported mesoporous silica. In other words, it was confirmed that antibacterial activity was obtained by combining ethanol and platinum-supported mesoporous silica, even though the doses of both alone did not show antibacterial activity.
  • Test result 2 Based on the results of the above evaluation result 1, the amount of ethanol dropped that would result in antibacterial activity in the presence of a given amount of platinum-loaded mesoporous silica was investigated. The results are shown in Table 3 below.
  • the amount of ethanol dropped onto the qualitative filter paper was set to 0 ⁇ L to 1000 ⁇ L, and the amount of platinum-loaded mesoporous silica added was set to 0g or 1.0g, and the samples were stored at a constant temperature.
  • the minimum amount of ethanol dropped that demonstrated antibacterial activity in the presence of 1.0g of platinum-loaded mesoporous silica was 75 ⁇ L (for Penicillium digitatum: Example (2)) or 50 ⁇ L (for Cladosporium sp.: Example (1)).
  • the measured values of the ethanol concentration in the gas phase inside the pouch bag in the test group where 50 ⁇ L of ethanol was dropped onto the qualitative filter paper were 310 Volppm, 307 Volppm, and 293 Volppm.
  • the minimum amount of ethanol dropped that demonstrated antibacterial activity in the absence of platinum-loaded mesoporous silica was more than 1000 ⁇ L (for Penicillium digitatum: Comparative Example (6)) and 1000 ⁇ L (for Cladosporium sp.: Comparative Example (6)).
  • no antibacterial activity was obtained with only 1.0 g of platinum-loaded mesoporous silica (Comparative Example 1).
  • Test result 3 The amount of platinum-supported mesoporous silica added that exhibits antibacterial activity in the presence of ethanol was investigated. The results are shown in Table 4 below. For one type of mold, the amount of ethanol dropped onto the qualitative filter paper was set to 0 ⁇ L or 250 ⁇ L, and the amount of platinum-supported mesoporous silica added was set to 0 g, 0.01 g, 0.07 g, or 1.0 g, and the samples were stored at a constant temperature. The minimum amount of platinum-supported mesoporous silica added that exhibits antibacterial activity in the presence of ethanol was 0.01 g (Example A).
  • Test result 4 The presence or absence of antibacterial activity against yeast and bacteria in the presence of ethanol and platinum-loaded mesoporous silica was investigated. The results are shown in Table 5 below. Antibacterial activity was observed against all tested yeasts and bacteria when 600 ⁇ L of ethanol was dropped onto qualitative filter paper and 1.0 g of platinum-loaded mesoporous silica was added (Example (A)). In other words, it was confirmed that high antibacterial activity can be obtained not only against mold but also against yeast and bacteria by combining the two.
  • Antibacterial activity evaluation test (antibacterial test on mandarin oranges) In the above “1. Antibacterial activity evaluation test”, the bacteria was smeared and inoculated on the agar medium to evaluate the antibacterial activity, but in this test, the antibacterial activity was evaluated using mandarin oranges inoculated with mold instead of agar medium inoculated with bacteria.
  • Test sections in which the same level of growth was observed as in the test section not containing platinum-loaded mesoporous silica were defined as having no antibacterial activity (+), and test sections in which no growth was clearly observed compared to the test section not containing platinum-loaded mesoporous silica were defined as having antibacterial activity (-).
  • Each of the 1.0 g catalysts placed on a plastic tray was placed in a gas bag (Frec Sampler (R) bag (F type)) together with a Kimwipe soaked with 2 mL of ethanol, and the gas bag was heat-sealed.
  • the sealed gas bag was left in a room temperature environment, and the amount of peracetic acid after 7 days was measured using a portable gas detector (D16) manufactured by Ati Co., Ltd.
  • Table 7 shows the physical properties of "platinum-supported mesoporous silica,”"Pt/CARiACTG-6,” and “FT-eco,” as well as the measurement results of the amount of peracetic acid after 7 days.
  • the concentration of peracetic acid detected in "Platinum-loaded mesoporous silica” was 0.21 ppm, and in Pt/CARiACT G-6, 0.03 ppm, while in FT-eco, the concentration was 0 ppm. It was confirmed that platinum-loaded mesoporous silica and Pt/CARiACT G-6 effectively generate peracetic acid, which has a strong antibacterial effect.

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WO2025249509A1 (ja) * 2024-05-29 2025-12-04 三菱ケミカル株式会社 白金族元素担持シリカ

Citations (4)

* Cited by examiner, † Cited by third party
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JP2003165717A (ja) * 2001-03-09 2003-06-10 Mitsubishi Chemicals Corp シリカゲル
JP2019085336A (ja) * 2017-11-01 2019-06-06 株式会社ファンケル 抗菌剤
JP2019136655A (ja) * 2018-02-09 2019-08-22 株式会社フルヤ金属 抗菌用多孔質材料及びそれを含む抗菌加工製品、並びにそれを用いた抗菌方法
JP2019137637A (ja) * 2018-02-09 2019-08-22 株式会社フルヤ金属 防カビ用多孔質材料及びそれを含む防カビ加工製品、並びにそれを用いた防カビ方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003165717A (ja) * 2001-03-09 2003-06-10 Mitsubishi Chemicals Corp シリカゲル
JP2019085336A (ja) * 2017-11-01 2019-06-06 株式会社ファンケル 抗菌剤
JP2019136655A (ja) * 2018-02-09 2019-08-22 株式会社フルヤ金属 抗菌用多孔質材料及びそれを含む抗菌加工製品、並びにそれを用いた抗菌方法
JP2019137637A (ja) * 2018-02-09 2019-08-22 株式会社フルヤ金属 防カビ用多孔質材料及びそれを含む防カビ加工製品、並びにそれを用いた防カビ方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025249509A1 (ja) * 2024-05-29 2025-12-04 三菱ケミカル株式会社 白金族元素担持シリカ

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