WO2009104670A1 - Agent antimicrobien et antiviral et son procédé d'utilisation - Google Patents
Agent antimicrobien et antiviral et son procédé d'utilisation Download PDFInfo
- Publication number
- WO2009104670A1 WO2009104670A1 PCT/JP2009/052866 JP2009052866W WO2009104670A1 WO 2009104670 A1 WO2009104670 A1 WO 2009104670A1 JP 2009052866 W JP2009052866 W JP 2009052866W WO 2009104670 A1 WO2009104670 A1 WO 2009104670A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antibacterial
- antiviral agent
- particles
- antiviral
- ultrafine
- Prior art date
Links
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Images
Classifications
-
- 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
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- 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
- A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
- A01N63/10—Animals; Substances produced thereby or obtained therefrom
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3472—Compounds of undetermined constitution obtained from animals or plants
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/358—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/56—Materials from animals other than mammals
- A61K35/618—Molluscs, e.g. fresh-water molluscs, oysters, clams, squids, octopus, cuttlefish, snails or slugs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/12—Antivirals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/12—Antivirals
- A61P31/14—Antivirals for RNA viruses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/12—Antivirals
- A61P31/14—Antivirals for RNA viruses
- A61P31/16—Antivirals for RNA viruses for influenza or rhinoviruses
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Definitions
- the present invention relates to an antibacterial and antiviral agent, and more particularly to an antibacterial and antiviral agent composed of baked ultrafine particles derived from shells and a method for using the same.
- Shellfish shells such as scallops and oysters are used because they generate hundreds of thousands of tons per year, and more than 90% by mass of the components are calcium carbonate, so they are used in many ways as a natural calcium source. Yes.
- powder obtained by firing and pulverizing shells is listed as a food additive under the name of “shells calcined calcium”.
- shells calcined calcium since it has a bactericidal and sterilizing effect, it is also used as a processing aid for sterilization washing.
- Patent Document 1 discloses an antibacterial agent obtained by firing a shell of shellfish shell in an inert gas atmosphere at a final reached temperature of 900 ° C., and has a maximum particle size of 100 ⁇ m or less after pulverization and an average particle size of 1 Antibacterial agents that are ⁇ 50 ⁇ m are described.
- Patent Document 2 describes a bacterial inhibitor in which a scallop shell is fired at 600 ° C. to 700 ° C., and the pulverized product has a particle size of 5 mm or less, preferably 10 ⁇ m or less.
- Patent Document 3 describes a virus reducing agent comprising a powder having an average particle size of 10 ⁇ m or less obtained by baking oyster shells at 650 ° C. or higher.
- the presence of silicon, iron, manganese, etc. in the fired shell is important for the generation of active oxygen species, and the fired shell is a mixture of calcium oxide and calcium carbonate. Therefore, it is said that the firing conditions are preferably within a specific range.
- the average particle size of the burned material of the shell is on the order of ⁇ m.
- Patent Document 1 describes an antibacterial agent having an average particle diameter of 1 to 50 ⁇ m
- Patent Document 2 describes a bacterial inhibitor having an average particle diameter of 10 ⁇ m or less.
- the upper limit value of the average particle diameter is mostly described in terms of ⁇ m or less as in Patent Document 2, and in this case, it can be read so as to include particles in the order of nm. Actual data are only described for particles on the order of ⁇ m.
- an object of the present invention is to provide an antibacterial and antiviral agent having a high antibacterial and antiviral effect that can be contained in various products and used for various purposes.
- the object is to provide an antibacterial and antiviral agent having a high antibacterial and antiviral effect.
- the present inventor can control the particle size of the primary particles to a size on the order of nm by adding a device to the pulverization method of the fired product of the shell.
- the particle size distribution can be sharpened and particles having a uniform particle shape can be obtained with good reproducibility.
- the antibacterial and antiviral action of the fired product of the shell is found to be extremely increased, and the present invention. It came to complete.
- the suspension of ultrafine particles obtained by the above ultrafine pulverization is used as it is, or when it is used without containing a dispersant or a pH buffering agent. Furthermore, the inventors have found that even better dispersibility and antibacterial and antiviral effects can be exhibited, and have completed the present invention.
- the present invention relates to an antibacterial antivirus characterized in that it is ultrafine particles obtained by firing and ultrafinely pulverizing a shell, and the number average length (a) in the minor axis direction of the primary particles is 10 nm to 100 nm.
- An agent is provided.
- the antibacterial and antiviral agent is provided in which the number average length (b) of primary particles in the major axis direction is 40 nm to 200 nm.
- the present invention also provides the antibacterial and antiviral agent described above, which is ultrafine particles obtained by firing and ultrafinely pulverizing a shell, wherein the primary particles are manufactured so as to have a certain particle size distribution. It is to provide.
- the shell is preliminarily pulverized and then fired, and then classified so that the 90% volume particle size is 30 ⁇ m or less, so that the volume average particle size is in the range of 0.5 ⁇ m to 10 ⁇ m.
- the antibacterial and antiviral agent is characterized in that it is produced by pulverization and then ultrafine pulverization by a wet method.
- the present invention also provides an antibacterial antiviral agent suspension characterized by suspending the above antibacterial antiviral agent.
- the present invention is a method of using the above antibacterial antiviral agent or the above antibacterial antiviral agent suspension, wherein the suspension state of the dispersion obtained by ultrafine pulverization by a wet method is substantially reduced.
- the present invention provides a method for using an antibacterial antiviral agent characterized by being used while being held.
- the ultrafine particles obtained by calcining and ultra-pulverizing the shell of the present invention have primary particles having a smaller, uniform and narrow particle size distribution than the conventional ones, so that the antibacterial is superior to the conventional ones. An antiviral effect can be exhibited.
- an antibacterial and antiviral agent having a high antibacterial and antiviral effect and a method for using the antibacterial and antiviral agent, which can be used as a substitute for conventionally used hypochlorite, for example.
- the antibacterial and antiviral agent of the present invention has a controlled particle size, it is possible to eliminate variations in quality among production lots of such products when used in various products for various applications. is there.
- FIG. 1 is an antibacterial and antiviral agent of the present invention, and is a view showing an SEM photograph (magnified 100,000 times) of ultrafine particles A having primary spherical particles (Production Example 1). It is a figure which shows the number distribution of the length (a) of a minor axis direction, and the length (b) of a major axis direction (it does not distinguish since it is equal) of the ultrafine particle A in which primary particles are substantially spherical (Production Example 1). .
- - ⁇ - Fine particle a,- ⁇ -: Fine particle b,- ⁇ -: Ultra fine particle A It is a figure which shows the suspension sample density
- - ⁇ - Fine particle a,- ⁇ -: Fine particle b,- ⁇ -: Ultra fine particle A
- the antibacterial and antiviral agent of the present invention is an ultrafine particle having primary particles obtained on the order of nm, which is obtained by subjecting a shell to pre-grinding and baking treatment, and then undergoing a grinding step. That is, the antibacterial and antiviral agent of the present invention is ultrafine particles obtained by firing and ultrafinely pulverizing shells, and the number average length (a) in the minor axis direction of the primary particles is 10 nm to 100 nm.
- the shell used in the present invention is not particularly limited as long as it is a shell rich in calcium carbonate having a certain crystal structure, but it is preferably available in large quantities, and examples include shells such as scallops, sea bream, and oysters. be able to.
- scallop has the highest production volume, and more than 98% of its components are calcium carbonate with a regular crystal structure, high whiteness, and high production volume. Since various contaminants such as protein are purified, the content of impurities is small, and the calcium carbonate crystals of scallop shells are orthorhombic, so the pulverized material before firing should be cemented like limestone. Since it has many advantages such as not causing it, it can be suitably used in the present invention.
- the number average length (a) in the minor axis direction of the primary particles is 10 nm to 100 nm.
- the thickness is preferably 15 to 90 nm, particularly preferably 20 to 80 nm. If the number average length (a) of the primary particles in the minor axis direction is too small, it may take too much time and cost for pulverization, or may easily aggregate and be difficult to handle. On the other hand, if it is too large, sufficient antibacterial and antiviral effects may not be obtained.
- the shape of the primary particles is not particularly limited and can be any shape from acicular to spherical.
- the number average length (b) in the major axis direction of the primary particles is preferably 40 nm to 200 nm. More preferably, it is 45 to 150 nm, and particularly preferably 50 to 120 nm.
- the number average length (b) in the major axis direction of the primary particles is too small, it may take too much time and cost for pulverization, or may easily aggregate and be difficult to handle. On the other hand, if it is too large, sufficient antibacterial and antiviral effects may not be obtained.
- the number average length (a) in the minor axis direction and the number average length (b) in the major axis direction of the primary particles are a scanning electron microscope (hereinafter referred to as “300,000 times to 300,000 times). Based on the photograph (abbreviated as “SEM”), randomly select 20 or more primary particles photographed there, and measure the length in the major axis direction and the length in the minor axis direction. Obtained by taking an arithmetic mean. In the light scattering method, measurement cannot be performed because the primary particles are orderly smaller than the wavelength of the measurement light.
- the shape of the primary particles obtained by firing and ultrafinely pulverizing the shell is not particularly limited, and can be any shape such as a needle shape, a rod shape, a bowl shape, and a spherical shape.
- FIGS. 1 and 2 show examples of antibacterial and antiviral agents having substantially spherical primary particles
- FIGS. 3 and 4 show examples of antibacterial and antiviral agents having rod-like primary particles.
- the antibacterial and antiviral effect of the present invention is extremely high compared to the antimicronized antiviral agent which is not micronized or whose primary particle shape is not controlled.
- the longest “passing length” among the particles is referred to as “major axis length”.
- the shorter “passing length” in the direction perpendicular to it is defined as “the length in the minor axis direction”.
- the number of ultrafine particles in which the length of the primary particles in the minor axis direction falls within the range of a / 2 to 2a is preferably 50% by number or more, It is more preferably at least several percent, particularly preferably at least 70 percent, more preferably at least 80 percent, and most preferably at least 90 percent.
- “a” indicates the number average length of the primary particles in the minor axis direction.
- the number of ultrafine particles in which the length of primary particles in the major axis direction falls within the range of b / 2 to 2b is preferably 50% by number or more of the total. 60% by number or more, more preferably 70% by number or more, still more preferably 80% by number or more, and most preferably 90% by number or more.
- “b” represents the number average length of primary particles in the major axis direction.
- the number of ultrafine particles falling within the range of “a / 2 to 2a” or “b / 2 to 2b” being equal to or greater than a certain value means that the particle size distribution is sharply controlled.
- 20 or more randomly selected primary particles were randomly selected based on the SEM photograph in the same manner as described above, and the length in the major axis direction and the length in the minor axis direction were each one. It is obtained by measuring and tabulating. If the number of ultrafine particles within the above range is too large, it may take too much time and cost for pulverization and classification, or may easily aggregate and become difficult to handle. On the other hand, when the amount is too small (when the particle size distribution is broad), sufficient antibacterial and antiviral effects cannot be obtained, or quality variation among production lots of products using the antibacterial and antiviral agent of the present invention increases. Sometimes.
- FIG. 1 shows a substantially spherical primary particle.
- the “number average length (a) in the minor axis direction” and the “number average length (b) in the major axis direction” of the primary particles are both 70 nm. is there.
- the number of ultrafine particles falling within the range of a / 2 to 2a and the range of b / 2 to 2b is 99% of the total.
- a and b may be easily adjusted to such a length, and are preferably 50 nm to 100 nm, and particularly preferably 60 nm to 90 nm.
- FIG. 3 shows rod-shaped particles.
- the “number average length (a) in the minor axis direction” of the primary particles is 25 nm
- the “number average length (b) in the major axis direction” is 50 nm. It is.
- the number of ultrafine particles falling within the range of a / 2 to 2a is 100% of the total
- the number of ultrafine particles falling within the range of b / 2 to 2b is 98%.
- a may be easily adjusted to such a length, and is preferably 10 nm to 40 nm, and particularly preferably 15 nm to 30 nm.
- b is likely to have such a length, and is preferably 40 nm to 180 nm, and particularly preferably 45 nm to 150 nm.
- the antibacterial and antiviral agent of the present invention is preferably ultrafine particles, and the primary particles thereof are manufactured so as to have a certain particle size distribution. “Controlled” refers to setting pulverization conditions such as a pulverizer, a pulverization method, and a dispersion time by paying attention to the particle size distribution of primary particles.
- the number average length (a) in the minor axis direction of the primary particles is limited, but the average particle size of the secondary particles formed by aggregation of the primary particles is not particularly limited. Absent. This is probably because the size of primary particles is related to the antibacterial and antiviral effects.
- the secondary particles usually have a number average particle size of 150 nm to 5000 nm (5 ⁇ m), preferably 200 nm to 3000 nm (3 ⁇ m), and more preferably 300 nm to 1000 nm (1 ⁇ m).
- the volume average particle size of the secondary particles is not particularly limited, and is usually 300 nm to 20000 nm (20 ⁇ m), preferably 400 nm to 5000 nm (5 ⁇ m), and more preferably 500 nm to 2000 nm (2 ⁇ m).
- the average particle size of the secondary particles is measured by the light scattering method and is defined by the value thus measured.
- the antibacterial and antiviral agent of the present invention may be used as a powder, or may be used in a suspended state in a dispersion medium such as water or an organic solvent.
- a dispersion medium such as water or an organic solvent.
- the antibacterial and antiviral effects of the present invention can be obtained even if the secondary particles are further aggregated to form aggregated particles.
- the suspension state of the dispersion produced by ultra-fine pulverization is substantially reduced. It is preferable that the antibacterial antiviral agent of the present invention is used while being held.
- the average particle size of the secondary particles at that time is not particularly limited, but the above range is preferable.
- the antibacterial and antiviral agent of the present invention is a nano-order ultrafine particle having a specific primary particle size, it is preferable to adopt a specific manufacturing process as shown below in order to manufacture it.
- the antibacterial and antiviral agent of the present invention is preferably an ultrafine particle, and is produced by controlling as follows so that the primary particles have a certain particle size distribution.
- the shell may be baked as it is, but it is preferable to first perform calcination after preliminary pulverization until the particle diameter is about several mm.
- the heating efficiency during firing of shell particles is improved, and the conversion from calcium carbonate to calcium oxide, which is one of the purposes of firing, goes smoothly into the powder. Proceed to.
- particles with a large number of pores are formed in the porous structure, and as a result, the particles are easily collapsed, and are easily crushed along with taking-out or transporting. The particles are likely to be small enough to be supplied.
- the preliminary pulverization method is not particularly limited, but a method of crushing manually or using a crusher, a hammer mill or the like is preferable.
- baking is a treatment in which at least a part of calcium carbonate, which is a component of the shell, is converted into calcium oxide by heating.
- what is obtained by baking may be hereinafter referred to as “baked product”.
- the firing method and firing conditions in the present invention are not particularly limited, but the firing temperature is preferably 600 ° C to 1400 ° C, more preferably 700 ° C to 1300 ° C, particularly preferably 800 ° C to 1200 ° C. Most preferably, it is 1000 ° C to 1100 ° C.
- the firing time depends on the firing conditions and is not particularly limited, but is preferably 30 minutes to 15 hours, more preferably 1 hour to 10 hours, particularly preferably 1.5 hours to 6 hours, and most preferably 2 hours to 4 hours. It's time. If the firing temperature is too high or the firing time is too long, vitrification may occur, and it may not be necessary and disadvantageous in cost.
- the firing temperature is too low or the firing time is too short, calcium oxide may not be sufficiently produced from calcium carbonate, which is a component of the shell, and the antiviral effect of the present invention may not be exhibited.
- the pulverization may not be sufficiently performed, and it may be difficult to obtain a product having a predetermined average particle diameter.
- the atmosphere during firing may be any of air, inert gas such as nitrogen, and vacuum, and is not particularly limited. However, firing in air is preferable because calcium carbonate in the shell easily converts to calcium oxide. .
- particles fired under the above firing conditions give particularly good results regarding antibacterial and antiviral effects compared to those fired under other firing conditions.
- Such firing conditions are thought to be because the influence on the subsequent pulverization process, the influence on the surface state of the particles, the change in the crystal structure, and the like are related to the antibacterial and antiviral effects.
- the particles after firing may be finely pulverized as they are, or may be “pulverized prior to ultrafine pulverization” as they are, but before entering the pulverization step, the 90% volume particle size is 30 ⁇ m or less. It is preferable that the pulverization is performed so that the subsequent pulverization can proceed efficiently and the subsequent pulverization provides a sharp particle size distribution. As described above, since the particles after firing are easily broken, the 90% volume particle size may be 30 ⁇ m or less without actively providing a classification step. In this case, the fired particles can be said to be “classified so that the 90% volume particle size is 30 ⁇ m or less”.
- classification is preferably performed so that the 90% volume particle size is 30 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
- the volume average particle size is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- the particle diameter of the particles is defined as that obtained according to a conventional method using a microtrack particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd.) which is a laser diffraction / scattered light type particle size distribution measuring apparatus.
- the classification step may or may not be provided, but the classification method in the case of providing is not particularly limited, a method of removing large particles by observing them, a method of sieving, and a method of classification by vibration of a container Etc.
- the method of sieving is preferable from the viewpoint of reliably removing coarse particles.
- pulverization means to reduce the average particle size, and the pulverization may be performed only once or twice or more, but the particle size is gradually reduced in two or more steps. However, it is preferable in that it can be efficiently reduced and a sharp particle size distribution can be easily obtained.
- the final pulverization is referred to as “ultra fine pulverization”
- the previous pulverization non-final pulverization
- fine pulverization those obtained by pulverization
- those obtained by pulverization are referred to as “ultrafine particles” and “fine particles”, respectively.
- ultrafine pulverization can be performed by a wet bead mill method, which will be described later, and it is possible to obtain the antibacterial and antiviral agent of the present invention in which the primary particles are on the order of nm even if the pulverization step is one stage.
- the particles are first adjusted to a specific particle size range in a fine pulverization step and then subjected to ultrafine pulverization by a wet method or the like. More preferably. That is, it is particularly preferable that at least the volume average particle size is first finely pulverized so as to be in the range of 0.1 ⁇ m to 30 ⁇ m, and then further ultrafinely pulverized until the particle size or particle shape is reached.
- the first “pulverization” is more preferably performed so that the volume average particle diameter is in the range of 0.5 ⁇ m to 10 ⁇ m, particularly preferably in the range of 0.7 ⁇ m to 8 ⁇ m. It is more preferable to carry out so that it may become the range of 5 micrometers. By reducing the volume average particle size to this range in the fine pulverization step, it becomes easy to finally pulverize into the above-mentioned particle size and particle shape in the ultrafine pulverization step.
- volume average particle diameter is measured by a laser particle size analyzer CILAS920 manufactured by CILAS, which is a laser diffraction / scattered light type particle size distribution measuring apparatus, and is defined by the volume average particle diameter measured as such.
- the pulverization method is not particularly limited as long as particles having a target particle diameter can be obtained, and may be a dry method or a wet method.
- the dry method include a method using a dry pulverizer such as a dry ball mill, a bead mill, a jet mill, or a crusher.
- the dry method include a method using a wet pulverizer such as a wet ball mill, a bead mill, a triple roll, a planetary mixer, and an optimizer (manufactured by ITOCHU Corporation).
- the dry method is not necessary for the subsequent ultrafine pulverization, such as replacement of the dispersion medium, and the subsequent ultrafine particle size is relatively sharp. This is preferable because it is suitable for grinding.
- the method using a jet mill is particularly preferable from the viewpoints similar to the above, a high recovery rate of fine particles, and a low generation of heat during pulverization.
- the processing time for pulverization can be appropriately set by confirming the particle size of the obtained particles.
- the antibacterial and antiviral agent of the present invention is ultrafine particles obtained by firing and ultrafinely pulverizing shells, and the primary particles are controlled so as to have a certain particle size distribution.
- the antibacterial and antiviral agent of the present invention is preferably produced by finely pulverizing and finally ultrafinely pulverizing.
- the ultra-fine pulverization may be performed by a wet method or a dry method, but the wet method is preferable in that a product having the above-described particle size and particle shape can be obtained.
- the method using a wet bead mill can obtain ultrafine particles having the aforementioned particle size, particle size distribution, particle shape, etc., does not require the use of a polymer to obtain high viscosity, and requires other additives. This is particularly preferable because it does not pulverize in water.
- the bead diameter in the wet bead mill is not particularly limited, but it is preferable to use beads having a bead diameter selected from the range of 0.05 mm to 0.5 mm. Particularly preferred are beads having a bead diameter selected from the range of 0.1 mm to 0.4 mm. If the bead diameter is too large, the particle size may not be reduced. On the other hand, if the bead size is too small, it may not be pulverized efficiently. In any case, ultrafine particles having the above-described particle size distribution, particle shape, etc. are obtained. It may be difficult.
- the material of the beads is not particularly limited, and those usually used in a normal wet bead mill are used.
- steel, zirconia, silica, stainless steel, glass and the like can be mentioned.
- the primary particles are sufficiently pulverized, and smaller and uniform primary particles can be obtained.
- an antibacterial and antiviral agent in which the intended primary particles are effectively finely pulverized to the order of nm and are homogenized in a narrow range of particle size distribution.
- the concentration of the suspension is 2 to 25% by mass (particularly preferably 3 to 20% by mass); Is water, ethanol, n-propanol, isopropanol, 1,3 butanediol, propylene glycol, glycerin or the like or a mixture thereof; dispersion medium is zirconia beads or silica beads; treatment time is 30 minutes to 30 hours (more preferably 1 hour) Up to 20 hours, particularly preferably from 2 hours to 10 hours); bead filling rate of 80 to 120% (preferably about 100%); for example, when the charging amount is 5 kg, the rotational peripheral speed is 1 to 50 m / sec (preferably 3 -15 m / sec); rotation speed is 100 to 2000 rpm (preferably 400 to 1200 rpm). Regarding the rotational peripheral speed and the rotational speed, it is preferable to adjust the above range according to the amount of ultrafine grinding.
- the “ultrafine particles of the order of nm in which the size of primary particles is limited” constituting the antibacterial and antiviral agent of the present invention obtained through the above steps is a uniform particle size distribution and a uniform particle shape that were not previously available It can be confirmed by an SEM photograph or the like. That is, the antibacterial and antiviral agent of the present invention is different from the fine powder having a very broad particle size distribution of Non-Patent Document 3, for example, even if it is substantially spherical particles (FIGS. 1 and 3), 4), the SEM photographs in FIGS. 1 and 3 and the particle size distributions in FIGS. 2 and 4 show that the antibacterial and antiviral agents are composed of primary particles having a uniform particle size and a uniform particle shape. It can be confirmed from.
- the particle size, particle shape, and particle size distribution are determined not only by the above-mentioned ultrafine grinding conditions, but also by controlling the time at each rotational speed, the amount of water added during the ultrafine grinding, the rotational peripheral speed, etc. To control.
- the antibacterial and antiviral agent of the present invention can be used as a powder or as a dispersion liquid dispersed in a dispersion medium.
- the antibacterial and antiviral agent of the present invention When used as a dispersion, the antibacterial and antiviral agent of the present invention is characterized in that dispersibility can be maintained without using a dispersant such as a surfactant as a basic property. Therefore, since the antibacterial antiviral agent suspension in which the antibacterial antiviral agent of the present invention is suspended can be used without blending a dispersant, the various uses of the antibacterial antiviral agent of the present invention are taken into consideration. Then, it is preferable that a dispersing agent is not included substantially.
- the antibacterial antiviral agent suspension obtained by suspending the antibacterial antiviral agent of the present invention is substantially free of an agent having a pH buffering action in the suspension. It is preferable for effective display. For example, as a result of comparing the action against Escherichia coli and the action against influenza virus A type PR8 strain when using physiological saline as a dispersion medium of 0.15% by mass suspension and using PBS, in both cases Anti-E. Coli and anti-influenza virus type A PR8 strains were better when suspended in saline.
- the concentration of ultrafine particles in the suspension varies depending on the target bacterial species, the purpose of application, the application time and the usage state at the time of application in relation to the purpose, 0.0001% by mass to 20% by mass is preferable, 0.001% by mass to 10% by mass is more preferable, and 0.01% by mass to 5% by mass is particularly preferable.
- 0.0001% by mass to 20% by mass is preferable
- 0.001% by mass to 10% by mass is more preferable
- 0.01% by mass to 5% by mass is particularly preferable.
- the antibacterial and antiviral agent suspension obtained by suspending the antibacterial and antiviral agent of the present invention may be used as it is in a dispersed state by diluting the dispersion obtained by ultrafine pulverization, if necessary. This is preferable in that it can be used while maintaining a good dispersion state. Once the powder is made into powder or the dispersion medium is replaced, it may not be possible to return to a good dispersion state or the antibacterial and antiviral effects may not be sufficiently obtained.
- a method for using the antibacterial and antiviral agent of the present invention it is preferable to use the antibacterial and antiviral agent while maintaining the suspended state of the dispersion obtained by ultrafine pulverization by a wet method.
- the bacterial species to which the antibacterial and antiviral agent of the present invention is applied is not particularly limited because the antibacterial and antiviral agent of the present invention does not exhibit antibacterial properties by attacking a specific part of the bacterium. be able to.
- the antibacterial species For example, Escherichia coli, Salmonella, and the like are very sensitive, and then the sensitivity decreases in the order of Pseudomonas aeruginosa and Staphylococcus aureus.
- the virus to which the antibacterial and antiviral agent of the present invention is applied is not limited to a specific virus, such as restriction by properties such as the presence or absence of an envelope, as in the case of the applied bacterial species.
- the antibacterial and antiviral agent of the present invention can be applied to viruses belonging to any of the above families.
- paramyxoviridae measles virus, orthomyxoviridae influenza virus, coronaviridae SARS coronavirus It is particularly preferable to be applied to Norovirus of the Caliciviridae family.
- the use of this drug for emerging infectious diseases caused by such viruses, zoonotic diseases, and new virus infectious diseases is particularly preferable in that the spread of these infectious diseases with few effective therapeutic agents can be prevented. .
- the infectious titer can be significantly reduced by treatment in a short time for the caliciviridae norovirus that does not have an envelope and is not lipophilic (Examples).
- 2 See data for feline calicivirus as an alternative to norovirus).
- Viruses that do not have an envelope and are not lipophilic are known to be highly resistant to various inactivation conditions. For example, 10 5 noroviruses (replaced by feline calicivirus) at 56 ° C. for 3 minutes. It is reported that the infectivity titer may not be reduced by about 1/300 even after treatment for 1 minute with a sodium hypochlorite solution with a final concentration of 1000 ppm (0.1% by mass).
- JCDoultree et al Inactivation of Feline Calicivirus, a Norwalk Virus Surrogate, Journal of Hospital Infection (1999) 41: 51-57].
- the “ultrafine particles whose number average length (a) in the minor axis direction of primary particles is 10 nm to 100 nm” of the present invention is the final concentration of 4 ⁇ 10 6 feline calicivirus infectivity. It has been confirmed that a significant effect of reducing the mass to 1/5000 by treatment for 0.5% by weight for 30 seconds and 1/10000 by treatment for 1 minute (Example 2).
- the sodium hypochlorite 1000 ppm solution corresponds to a concentration of 1/50 that of a commercially available bleach solution, and is highly irritating and toxic to the human body.
- the 0.5% by mass suspension of the antibacterial and antiviral agent of the present invention has low cytotoxicity and high safety.
- the antibacterial and antiviral agent of the present invention is contained in various materials and used as various antibacterial and antiviral materials.
- Such an antibacterial and antiviral material may be solid, liquid, or a mixture or composite thereof as long as it contains the antibacterial and antiviral agent of the present invention.
- Such antibacterial and antiviral materials include feeds for livestock such as pigs, cattle and sheep; feed for poultry such as chickens, geese and ducks; filters for air conditioners, air cleaners, vacuum cleaners, etc .; , Masks for work, etc .; adhesives; wiping materials such as floor wiping materials, wall wiping materials, etc .; deodorants; kitchen materials; drugs for athlete's foot treatments, mouthwashes, infection prevention agents for pressure ulcers, etc .; Members such as woven fabrics and wall materials are preferred.
- the infectivity of viruses such as a microbe and influenza virus which contacted this filter, can be attenuated.
- viruses such as a microbe and influenza virus which contacted this filter
- the antibacterial and antiviral agent of the present invention is contained in the feed, infection by bacteria and viruses is prevented and a growth promoting effect is obtained.
- it is not particularly limited, but a method of mixing the powder of the antibacterial and antiviral agent of the present invention into the feed as it is, a method of mixing the suspension of the antibacterial and antiviral agent of the present invention with the feed, etc. are used.
- the antibacterial and antiviral agent of the present invention is contained in the feed, the antibacterial and antiviral agent of the present invention is contained in an amount of 0.005 to 0.5 parts by mass in terms of ultrafine particles with respect to 100 parts by mass of the feed. Preferably, 0.05 parts by mass to 0.3 parts by mass are mixed. If the content is too small, the antibacterial and antiviral effects may not be obtained. If the content is too large, no further effects may be obtained, cytotoxicity may occur, or the environment may be polluted.
- antibacterial and antiviral agents When used as a liquid containing antibacterial and antiviral agents, it can be used not only for wiping materials such as floor wiping agents, but also to feed animals as feed to prevent infection with bacteria and viruses. is there. Since this agent does not affect beneficial bacteria such as lactic acid bacteria, it can continue to be fed to domestic animals such as pets, pigs, cows, chickens, sheep, etc. It can inactivate viruses and protect human health as well as pets and livestock.
- the action and principle of the antibacterial and antiviral effect of the antibacterial and antiviral agent of the present invention are not clear, and the present invention is not limited to the scope of such action and principle, but the following may be considered. That is, as described above, assuming that the active oxygen species are related to the antibacterial and antiviral effect, the active oxygen species has a short lifetime, so that the effect is expected to be limited to the vicinity of the particle surface. Therefore, the appearance of the effect is considered to vary greatly depending on the size and shape of the particles and the difference in other fine conditions on the particle surface. Therefore, regarding the size of the particles constituting the antibacterial and antiviral agent, it is considered that the smaller one showed a stronger antibacterial and antiviral effect.
- the burned shellfish could have a sharp particle size distribution and a uniform particle shape by a specific pulverization method. It is done.
- a scallop shell from Aomori Prefecture was pre-ground using a dry ball mill to a particle size of about 5 mm and then fired in air at 1050 ° C. to 1100 ° C. for 3 hours.
- a part of the fired product was sieved with a 120 mesh sieve. Since it was extremely fragile, it was crushed during sieving, and there was hardly any fired product of shells remaining on the sieve.
- the volume particle size distribution of the particles under the sieve was measured, the 98% volume particle size was 30 ⁇ m, the 90% volume particle size was 12 ⁇ m, and the volume average particle size was 8 ⁇ m. Even if the classification operation was not particularly performed, the 90% volume particle size was 30 ⁇ m or less.
- the volume particle size distribution and the like were measured using a Microtrac particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.) according to the instruction manual.
- the particles under the above sieve were pulverized with a dry jet mill pulverizer (Aisin Nano Technology's NanoJet Mizer) to obtain fine particles.
- the volume average particle diameter of the fine particles was 1.8 ⁇ m.
- the volume average particle diameter was measured using a laser particle size analyzer CILAS920 manufactured by CILAS according to the instruction manual.
- FIG. 1 An SEM photograph of this ultrafine particle A is shown in FIG.
- the particle size distribution is shown in FIG.
- the number average length (a) in the minor axis direction of the primary particles of the ultrafine particles A calculated from FIGS. 1 and 2 was 70 nm.
- the number average length (b) in the major axis direction was also 70 nm.
- the number of ultrafine particles in which the lengths of the primary particles in the short axis direction and the long axis direction are within the range of a / 2 to 2a and b / 2 to 2b was 99% by number.
- the number average particle size of the secondary particles formed by the aggregation of the primary particles was 650 nm.
- Production Example 2 In Production Example 1, a suspension of ultrafine particles B was obtained in the same manner as in Production Example 1, except that the number of rotations and the additional amount of water were adjusted and pulverized for 10 hours.
- FIG. 1 An SEM photograph of this ultrafine particle A is shown in FIG.
- the particle size distribution is shown in FIG.
- the number average length (a) in the minor axis direction of the primary particles of the ultrafine particles B calculated from FIGS. 3 and 4 was 25 nm.
- the number average length (b) in the major axis direction was 50 nm.
- the number of ultrafine particles whose lengths in the minor axis direction and major axis direction of the primary particles are in the range of a / 2 to 2a and b / 2 to 2b are 100% by number and 94% by number, respectively.
- the number average particle diameter of the secondary particles formed by the aggregation of the primary particles was 600 nm.
- Comparative production example 1 The particles fired and sieved in the same manner as in Production Example 1 were treated with a dry bead mill grinder (manufactured by Ashizawa Finetech) for about 2 hours to obtain “fine particles a”.
- the volume particle size distribution of the “fine particles a” is shown in FIG. 5, and the number particle size distribution is shown in FIG. “Particle a” has a 10% (volume) particle size of 8.5 ⁇ m, a 50% (volume) particle size of 18.4 ⁇ m, a 90% (volume) particle size of 43.7 ⁇ m, and a volume average particle size of 18.4 ⁇ m.
- the 10% (number) particle size was 3.3 ⁇ m
- the 50% (number) particle size was 6.1 ⁇ m
- the 90% (number) particle size was 13.2 ⁇ m
- the number average particle size was 6.1 ⁇ m.
- Comparative production example 2 The particles fired and sieved in the same manner as in Production Example 1 were dispersed in water so as to be 10% by mass and passed 15 times at an injection pressure of 150 MPa using an optimizer (manufactured by Sugino Machine Co., Ltd.). Got. The number average particle diameter of “fine particles b” was 237 nm, and the volume average particle diameter was 670 nm.
- FIG. 7 shows an SEM photograph.
- Evaluation Example 1 [Evaluation of antiviral effect (measles virus)] A suspension of “ultrafine particles A” obtained in Production Example 1, a suspension of “fine particles a” obtained in Comparative Production Example 1, and a suspension of “fine particles b” obtained in Comparative Production Example 2 Were each adjusted to 5% by mass with sterilized physiological saline to obtain a “suspension sample”.
- Measles virus is a measles virus wild isolate MVi / Tokyo. JPN / 18.07 (genotype D5) was used. Grow with B95a cells and use 4 5.0 TCID50 / ⁇ L of measles virus solution.
- the antiviral effect of the three types of suspension samples was confirmed by confirming the measles virus infectivity titer indicated by the supernatant when mixed with the measles virus solution by the following TCID50 method (50% Tissue Culture Infective Dose). .
- ⁇ Measurement of measles virus infectivity titer by TCID50 method To 100 ⁇ L of measles virus solution (4 5.0 TCID50 / ⁇ L), the above three types of suspension samples were added to 0.2% by mass and 0.1% by mass, respectively, for 1 minute, 3 minutes, After 5 minutes and 10 minutes, after centrifugation at 13000 rpm for 30 seconds, the measles virus infectivity of each supernatant was measured by the following method.
- the measles virus infectivity was measured by monolayer culture of B95a cells in a 96-well flat-bottom plate, and the measles virus solution was RPMI1640 supplemented with 1% fetal bovine serum (FBS), stepwise diluted from 1/4 to 4 times. Then, the cytopathic effect after 1 week was observed, and the infectivity titer was measured by the Reed Menchen method.
- FBS fetal bovine serum
- Table 1 shows the infectivity titer measured one week after inoculating each supernatant.
- the infectious titer When added to a concentration of 0.1% by mass, in the ultrafine particles A, the infectious titer decreased to 42.25 after 1 minute contact, and the infectious titer disappeared after 3 minutes of contact. On the other hand, in the case of microparticles a, the infectivity titer slightly decreased to 42.5 at a contact time of 1 minute and 3 minutes, but did not disappear. Further, even if the fine particles b, the contact of one minute time 4 3.25 4 3 infectivity at a contact time of 3 minutes did not disappear in those slightly reduced.
- the effect of the present invention is that the ultrafine particles A do not simply remove the measles virus by adsorption or the like but have an action of reducing the infectivity of the measles virus itself.
- Evaluation example 2 [Evaluation of antiviral effect (influenza virus)] A suspension of “ultrafine particles A” obtained in Production Example 1, a suspension of “fine particles a” obtained in Comparative Production Example 1, and a suspension of “fine particles b” obtained in Comparative Production Example 2 Were each adjusted to 5% by mass with sterilized physiological saline to obtain a “suspension sample”.
- influenza virus As for influenza virus, influenza A / Panama / 2007/99 was inoculated into the chorioallantoic cavity of a chicken fertilized egg and the virus solution was collected. For 200 ⁇ L of influenza virus solution, add the above three types of suspension samples to the virus solution at 0.1%, 0.05%, and 0.025%, respectively, and centrifuge at 13000 rpm for 30 seconds. Qing's influenza virus hemagglutinin (HA) (hereinafter abbreviated as “HA antigen titer”) was measured.
- HA antigen titer Qing's influenza virus hemagglutinin
- the HA antigen titer was determined by measuring the agglutination titer using a 96-well U plate, 2-fold serial dilution with PBS, adding an equal amount of 0.5% chicken blood cells and reacting at room temperature for 1 hour.
- the suspension sample of ultrafine particles A ( ⁇ in FIG. 9) is fine particles a (FIG. 9).
- the HA antigen titer was smaller compared to the suspension samples of- ⁇ -) and fine particles b (- ⁇ -in FIG. 9). In 0.1%, was completely inactivated in ultrafine particles A and fine particles b suspension sample, the suspension sample particles a, HA antigen titer is not deactivated completely a 2 2.0 It was.
- feline calicivirus (F9 strain # 2) that can be cultured was used as an alternative because norovirus of the Caliciviridae family could not be cultured.
- the infectivity value was 4.0 ⁇ 10 6 PFU (number of infectious viruses) / 100 ⁇ L.
- CRFK cells (cat kidney cell lines) were used as cultured cells.
- the ultrafine particles B were examined under all conditions, and the fine particles a were examined only for 30 seconds with the control. Further, when the cytotoxicity of the particle solution was examined in the test, no cytotoxicity was observed at a concentration of 0.5% by mass used in the test.
- the infectivity titer was measured by the usual procedure according to the following procedure. That is, CRFK cells were seeded in a 6-well plate, and used after 7 days after the cells became confluent.
- the test virus solution was serially diluted 10-fold in a MEM medium without serum.
- 100 ⁇ L / well of the diluted virus solution was inoculated in two wells.
- the virus was adsorbed with a CO 2 incubator at 34 ° C. for 1 hour.
- 3 mL / well of an agar medium was added to each hole.
- the plate was inverted and cultured at 34 ° C. for 3 days.
- the infectivity titer rapidly decreased to about 1/5000 after 1 minute contact and about 1/10000 after 1 minute.
- the infectivity value was only reduced to 1/3000 after 0.5 minutes of contact.
- the ultrafine particle B sharply decreases the infectivity of feline calicivirus, which is a substitute for norovirus.
- the fine particles a were inferior to the ultrafine particles B, the infectious value was decreased, which is considered to be due to the high use concentration of 0.5% by mass.
- feline calicivirus In the case of feline calicivirus, it is not inactivated at all by heat treatment at 56 ° C for 3 minutes, and even when the 1000 ppm sodium hypochlorite high-concentration solution remains at a reduction of 1/300 infectivity in 1 minute treatment time In view of the fact that the infectivity titer can be reduced to 1/10000 by contact with ultrafine particles B for 1 minute, it indicates that ultrafine particles B are effective antiviral agents against norovirus. ing.
- Evaluation Example 4 Evaluation of antibacterial effect (E. coli, Salmonella, Staphylococcus aureus, Pseudomonas aeruginosa)]
- the ultrafine particle A obtained in Production Example 1 was adjusted to a suspension of 0.15%, and the viable cell count was measured after 15 seconds, 3 minutes, 10 minutes, and 30 minutes. The results are shown in Table 3. It was.
- Escherichia coli and Salmonella were reduced to 1/100 or less in 15 seconds and completely disappeared after 3 minutes.
- S. aureus it took 30 minutes to exert its effect, but it was finally effective.
- Pseudomonas aeruginosa almost completely in 5 minutes.
- the antibacterial and antiviral agent of the present invention is excellent in the effect of attenuating the infectivity against various infectious bacteria and viruses, and therefore contains an antibacterial and antiviral agent, including its use as an antibacterial and antiviral agent. It is widely used as antibacterial and antiviral materials such as filters and feeds.
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Abstract
L'invention concerne un agent antimicrobien et antiviral qui présente une activité antimicrobienne et antivirale élevée, qui est extrêmement sûr, qui est inodore, qui est plus respectueux de l'environnement, qui est capable de maintenir la fraîcheur de produits alimentaires, qui ne génère pas de substance dangereuse lors de son élimination par incinération ou analogue et qui peut être utilisé pour diverses applications en étant incorporé dans divers produits. L'agent antimicrobien et antiviral selon l'invention comprend des particules ultrafines obtenues par combustion et pulvérisation ultrafine de coquilles, la longueur moyenne en nombre (a) dans la direction du petit axe des particules primaires étant de 10 nm à 100 nm. L'invention concerne également un agent antimicrobien et antiviral fabriqué par combustion de coquilles après pulvérisation préliminaire, tamisage des coquilles brûlées de manière à ce que diamètre de particule à 90 % en volume devienne de 30 µm ou moins, pulvérisation fine du matériau tamisé de manière à ce que le diamètre de particule moyen en volume soit dans la plage allant de 0,5 µm à 10 µm, suivie d'une pulvérisation ultrafine supplémentaire par un procédé en voie humide.
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Cited By (10)
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WO2011058964A1 (fr) * | 2009-11-10 | 2011-05-19 | 株式会社かわかみ | Agent d'inactivation virale |
JP2011245399A (ja) * | 2010-05-25 | 2011-12-08 | Mikuni Color Ltd | 貝殻粉末分散用分散剤および貝殻粉末分散液 |
JP2012062257A (ja) * | 2010-09-14 | 2012-03-29 | Tahara Masanori | 貝殻焼成カルシウム粉体を用いた抗ウイルス材 |
JP2018024617A (ja) * | 2016-08-10 | 2018-02-15 | 株式会社J−Style | ホタテ貝焼成粉末、その混合液、製造方法、および保存方法 |
JP2020090624A (ja) * | 2018-12-06 | 2020-06-11 | 有限会社日革研究所 | アレルゲン低減化剤およびアレルゲン低減化方法 |
JP2020200278A (ja) * | 2019-06-11 | 2020-12-17 | 株式会社プラスラボ | 緑膿菌感染創の消毒剤又は創傷治癒剤 |
EP3789351A1 (fr) * | 2019-09-04 | 2021-03-10 | Wen-Lung Chin | Désodorisant d'eau et son procédé de fabrication |
EP3789348A1 (fr) * | 2019-09-04 | 2021-03-10 | Wen-Lung Chin | Agent de purification d'eau et son procédé de fabrication |
WO2022055311A1 (fr) * | 2020-09-10 | 2022-03-17 | 건국대학교 산학협력단 | Composition comportant de l'hydroxyapatite et de l'hydroxyde de calcium ayant une activité antibactérienne ou antivirale et son procédé de fabrication |
KR20220033962A (ko) * | 2020-09-10 | 2022-03-17 | 건국대학교기술지주 주식회사 | 항균 또는 항바이러스 활성을 갖는 수산화 인회석 및 이의 제조 방법 |
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WO2011058964A1 (fr) * | 2009-11-10 | 2011-05-19 | 株式会社かわかみ | Agent d'inactivation virale |
CN102612320A (zh) * | 2009-11-10 | 2012-07-25 | 株式会社川上 | 病毒灭活剂 |
AU2010319177B2 (en) * | 2009-11-10 | 2014-02-06 | Kawakami Co., Ltd. | Virus-inactivating agent |
CN102612320B (zh) * | 2009-11-10 | 2014-10-08 | 株式会社川上 | 病毒灭活剂 |
JP5763546B2 (ja) * | 2009-11-10 | 2015-08-12 | 株式会社かわかみ | ウイルス不活化剤 |
JP2011245399A (ja) * | 2010-05-25 | 2011-12-08 | Mikuni Color Ltd | 貝殻粉末分散用分散剤および貝殻粉末分散液 |
JP2012062257A (ja) * | 2010-09-14 | 2012-03-29 | Tahara Masanori | 貝殻焼成カルシウム粉体を用いた抗ウイルス材 |
JP2018024617A (ja) * | 2016-08-10 | 2018-02-15 | 株式会社J−Style | ホタテ貝焼成粉末、その混合液、製造方法、および保存方法 |
JP2020090624A (ja) * | 2018-12-06 | 2020-06-11 | 有限会社日革研究所 | アレルゲン低減化剤およびアレルゲン低減化方法 |
JP2020200278A (ja) * | 2019-06-11 | 2020-12-17 | 株式会社プラスラボ | 緑膿菌感染創の消毒剤又は創傷治癒剤 |
JP7302785B2 (ja) | 2019-06-11 | 2023-07-04 | 株式会社プラスラボ | 緑膿菌感染創の消毒剤又は創傷治癒剤 |
EP3789351A1 (fr) * | 2019-09-04 | 2021-03-10 | Wen-Lung Chin | Désodorisant d'eau et son procédé de fabrication |
EP3789348A1 (fr) * | 2019-09-04 | 2021-03-10 | Wen-Lung Chin | Agent de purification d'eau et son procédé de fabrication |
WO2022055311A1 (fr) * | 2020-09-10 | 2022-03-17 | 건국대학교 산학협력단 | Composition comportant de l'hydroxyapatite et de l'hydroxyde de calcium ayant une activité antibactérienne ou antivirale et son procédé de fabrication |
KR20220033962A (ko) * | 2020-09-10 | 2022-03-17 | 건국대학교기술지주 주식회사 | 항균 또는 항바이러스 활성을 갖는 수산화 인회석 및 이의 제조 방법 |
KR102546359B1 (ko) * | 2020-09-10 | 2023-06-28 | 건국대학교기술지주 주식회사 | 패각유래 수산화칼슘과 수산화 인회석 포함한 마이크로 입자를 이용한 항균 및 항바이러스용 필름의 제조 방법 |
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