WO2021230154A1 - Cooling medium, freezer, and method for producing frozen product - Google Patents

Cooling medium, freezer, and method for producing frozen product Download PDF

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Publication number
WO2021230154A1
WO2021230154A1 PCT/JP2021/017526 JP2021017526W WO2021230154A1 WO 2021230154 A1 WO2021230154 A1 WO 2021230154A1 JP 2021017526 W JP2021017526 W JP 2021017526W WO 2021230154 A1 WO2021230154 A1 WO 2021230154A1
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Prior art keywords
weight
powder
cooling medium
ethanol solution
aqueous ethanol
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PCT/JP2021/017526
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French (fr)
Japanese (ja)
Inventor
弘一 仁居
正彦 田中
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感動創出工場ジーンファクトリー株式会社
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Publication of WO2021230154A1 publication Critical patent/WO2021230154A1/en

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    • 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
    • A23L3/36—Freezing; Subsequent thawing; Cooling
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D3/00—Devices using other cold materials; Devices using cold-storage bodies

Definitions

  • the present invention relates to a method for manufacturing a cooling medium, a freezer and a frozen product, and more particularly to a method for manufacturing a cooling medium, a freezer and a frozen product for freezing such as food, cosmetics or medical articles.
  • the freezer has a brine-type freezer that freezes an object by immersing it in a liquid that has been cooled to below freezing point.
  • a brine composition has been proposed, characterized in that a mixture containing ethyl alcohol, water and propylene glycol is used as a brine for food (see, for example, Patent Document 1).
  • the present invention has been made in view of such a situation, and suppresses coagulation at a lower temperature so that an article can be frozen more safely and faster.
  • the cooling medium according to the first aspect of the present invention is a cooling medium that is stored in a container in a freezer and cooled, and is used as a liquid for freezing the article by immersing the article in it. It contains a powder obtained by crushing a product obtained by thermally decomposing seeds at 400 ° C. or higher and lower than 500 ° C., and a water-soluble silicon compound.
  • the powder may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution, and the water-soluble silicon compound may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution. ..
  • the powder When the powder is dispersed in an aqueous ethanol solution, the powder can be kept in a suspended state for 24 hours or more in a stationary state.
  • the powder can have a representative value of 10 ⁇ m or less, which indicates the center of the particle size distribution.
  • the powder can contain 15% by weight to 19% by weight of potassium and 1% by weight to 3% by weight of phosphorus.
  • the powder can generate a zeta potential of minus 0.5 mV in a pH 7 solution.
  • the powder can be made by crushing a product obtained by thermally decomposing seeds, which are beans.
  • the ethanol aqueous solution can contain less than 60% by weight of ethanol.
  • the freezer can store the cooling medium in the internal container.
  • a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 ° C. or higher and lower than 500 ° C. is mixed with an aqueous ethanol solution to prepare an aqueous ethanol solution.
  • a water-soluble silicon compound is mixed, and the ethanol aqueous solution in which the powder and the silicon compound are mixed is cooled to a temperature lower than 0 ° C. in a liquid state, the article is placed in a sealed container, and the article placed in the sealed container is placed. Immerse in a cooled aqueous solution of ethanol and freeze.
  • solidification can be suppressed at a lower temperature, and the article can be frozen more safely and faster.
  • FIG. 1 is a diagram illustrating the appearance of the freezer according to the embodiment of the present invention.
  • the freezer 1 is an example of a freezer, and is an integrated freezer having a substantially rectangular parallelepiped outer shape.
  • the freezer 1 incorporates a compressor, a condenser, an expansion valve, an evaporator, and the like, and a cooler is embedded in the inner wall of the freezer chamber, which will be described later, to cool the freezer chamber to a temperature lower than zero degrees Celsius.
  • the freezer 1 has a built-in compressor, condenser, expansion valve, evaporator, etc., and can be opened and closed freely with respect to the main body 11 having a freezing chamber inside and the main body 11 via a hinge (not shown). It includes a door 12 provided and a temperature controller 13 for adjusting the temperature in the freezing chamber.
  • the direction connecting the upper right and the lower left in FIG. 1 is the X-axis direction.
  • the direction connecting the lower right and the upper left in FIG. 1 indicates the Y-axis direction, and the vertical direction in FIG. 1 indicates the Z-axis direction.
  • FIG. 2 is a cross-sectional view of the freezer 1 showing a cross section in a plane defined by the X-axis and the Z-axis and along the position indicated by the AA'line in FIG.
  • a freezing chamber 31 which is a space for cooling
  • the lower side of the freezing chamber 31, that is, the main body 11 side is surrounded by a cooler 32 made of a steel plate.
  • a heat exchanger connected to a condensing unit 33 including a compressor, a condenser, an expansion valve, etc. by a pipe is provided on the surface of the cooler 32 facing the surface on the freezing chamber 31 side. There is.
  • the heat exchanger absorbs heat from the cooler 32, and the condenser of the condensing unit 33 exhausts heat. As a result, the freezing chamber 31 is cooled.
  • the outside of the cooler 32 is covered with a heat insulating material 34 made of polyurethane foam resin, a vacuum panel, or the like. Further, the door 12 is filled with a heat insulating material 35 made of a foamed polyurethane resin, a vacuum panel, or the like. That is, the entire freezing chamber 31 is surrounded by the heat insulating material 34 and the heat insulating material 35.
  • a container 36 is provided in the freezing chamber 31 of the freezer 1.
  • the container 36 is made of a highly heat-conducting material such as stainless steel or a galvanized steel plate.
  • a liquid cooling medium 37 is stored in the container 36.
  • the container 36 is formed in a tank shape.
  • the container 36 may be in the shape of a hemispherical ball or may be provided with a lid, as long as it can store the liquid cooling medium 37.
  • the container 36 is removable from the freezing chamber 31 of the freezer 1.
  • the freezer 1 is not limited to the integrated freezer, and may be any one that can be cooled to a desired temperature, and may be composed of a stationary freezer unit, a condensining unit, and a separate showcase or a freezer warehouse. It may be a vertical or horizontal industrial freezer. Further, the freezer 1 may be of any cooling method, and has a reciprocating type (reciprocal type) or a rotary capacity compression type, a centrifugal type (turbo type), an absorption type, a turbo type using an air refrigeration cycle, and a Pelche effect. It can be the electronic refrigerator or magnetic refrigerator used.
  • the cooling medium 37 is stored in a container 36 in the freezer 1 and cooled, and is used in a liquid state for freezing the article by immersing the article.
  • the cooling medium 37 contains an aqueous ethanol solution, a powder obtained by crushing a product obtained by thermally decomposing plant seeds, and a water-soluble silicon compound.
  • the ethanol aqueous solution is a mixture of ethanol (ethyl alcohol) and water in a predetermined ratio. Ethanol can dissolve various organic substances and is relatively less toxic among monohydric alcohols. In addition, ethanol can be miscible with water in any proportion. In the aqueous ethanol solution, the concentration of ethanol can be any value, for example, 10% by weight to 90% by weight.
  • the freezing point of the aqueous ethanol solution alone is -45.4 degrees Celsius.
  • the powder mixed with the aqueous ethanol solution is made by crushing the product of pyrolysis of plant seeds.
  • plant seeds are legumes such as adzuki beans, soybeans, green beans, peas, cowpeas, broad beans, chick beans, lentils or peanut seeds.
  • Plant seeds are pyrolyzed in a semi-enclosed electric furnace at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius.
  • the product obtained by thermally decomposing plant seeds is pulverized by a pulverizer such as a ball mill into a powder having a representative value of 10 ⁇ m or less, which indicates the center of particle size distribution.
  • semi-sealed means a state in which the oxygen partial pressure is reduced compared to the atmospheric atmosphere.
  • semi-sealing refers to a state in which the firing space and the outside are communicated with each other through gaps or small holes so that replacement of the atmosphere inside the firing space with the outside air is suppressed, as in a charcoal kiln.
  • the seeds of the plant are heated and thermally decomposed in a state where oxidation or combustion is suppressed.
  • a product obtained by thermally decomposing the plant seeds can be obtained.
  • Bincho charcoal has a hardness comparable to that of metal because it is fired at a high temperature of about 1,000 degrees Celsius.
  • a product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius is placed in a ball mill pot together with alumina balls and crushed by rotating the ball mill pot.
  • the powder obtained by grinding is sieved by a predetermined mesh.
  • FIG. 3 is a diagram showing a powder having a particle size of about 5 ⁇ m, taken at 10,000 times using a scanning electron microscope. It can be seen that the outer shape of the powder has no corners and is easily crushed. Further, the powder does not have fine pores.
  • FIG. 4 is a diagram showing an example of the result of component analysis of powder.
  • the ratio of the elements contained in the powder shown in FIG. 4 was determined by CHN elemental analysis (Elemental Analysis (Carbon, Hydrogen, Nitrogen)) and fluorescent X-ray analysis.
  • the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant, which is a small bean contains 66.5% by weight of carbon, 17.1% by weight of potassium, and 6.1% by weight.
  • Nitrogen 4.2% by weight hydrogen, 2.78% by weight phosphorus, 1.4% by weight calcium, 0.8% by weight magnesium, 0.5% by weight sulfur, 0.26% by weight It contains iron, 0.07% by weight zinc, 0.05% by weight manganese, 0.03% by weight silicon, 0.02% by weight aluminum and 0.01% by weight copper.
  • the product of pyrolyzing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius contains potassium and phosphorus, which results in hydrophilicity.
  • potassium is an alkali metal.
  • magnesium is contained in the product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius. Magnesium produces alkaline water.
  • the product obtained by thermally decomposing beans can be pulverized relatively easily, and a powder having a value at the center of the particle size distribution of 10 ⁇ m or less can be easily obtained.
  • the powder obtained by grinding the product of pyrolysis of plant seeds produces a zeta potential of minus 0.5 mV in a solution at pH 7. Therefore, the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant causes a unique chemical reaction such as binding to a substance having a positive potential such as a protein. Further, the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant generates a zeta potential of minus 0.5 mV in a solution of pH 7, so that they repel each other and easily disperse.
  • the particle size distribution of the powder obtained by pyrolyzing the seeds of a plant, which is a small bean, at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius by crushing it with a crusher such as a ball mill was measured.
  • the particle size distribution of the powder was measured by using a laser diffraction type particle size distribution measuring device that irradiates the particle group with laser light and obtains the particle size distribution by calculation from the intensity distribution pattern of the diffraction / scattered light emitted from the particle group. ..
  • the measurement range of the laser diffraction type particle size distribution measuring device is from 0.05 ⁇ m to 3,000 ⁇ m. The number of measurements is four.
  • FIG. 5 is a diagram showing the particle size distribution of the powder measured by the volume relative particle size distribution and the number relative particle size distribution.
  • the horizontal axis of FIG. 5 indicates the particle size ( ⁇ m) in a logarithm, and the vertical axis indicates the relative particle amount (%).
  • the average particle size (average value) is 7.4 ⁇ m, and the mode is 8.5 ⁇ m.
  • the median is 8.491 ⁇ m.
  • the average deviation is 0.373.
  • the average value, mode value, and median value are examples of representative values indicating the center of the particle size distribution, respectively.
  • the powder obtained by crushing the product obtained by thermally decomposing the seeds of the plant is crushed until the representative value indicating the center of the particle size distribution becomes 10 ⁇ m or less.
  • the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant can be crushed until the representative value indicating the center of the particle size distribution becomes 3 ⁇ m or more.
  • FIG. 6 is a diagram showing a state when a powder obtained by crushing a product obtained by thermally decomposing plant seeds is mixed with an aqueous ethanol solution.
  • the powder obtained by crushing the product obtained by thermally decomposing plant seeds has high wettability and quickly precipitates in an aqueous ethanol solution.
  • FIG. 7 is a diagram showing a state of an ethanol aqueous solution mixed with powder when 24 hours have passed in a stationary state.
  • the left side in FIG. 7 shows a state in which a powder obtained by crushing a product obtained by thermally decomposing plant seeds is dispersed in an aqueous ethanol solution and left standing for 24 hours.
  • the right side in FIG. 7 shows a state in which a powder made by crushing general charcoal is dispersed in an aqueous ethanol solution and left standing for 24 hours.
  • the cooling medium 37 0.1% by weight to 1.0% by weight of powder is mixed with the aqueous ethanol solution. According to the experiment, when 0.1% by weight or more of the powder was mixed with the aqueous ethanol solution, a decrease in the freezing point of the cooling medium 37 was observed. Further, according to the experiment, it was confirmed that when a powder exceeding 1.0% by weight was mixed with the aqueous ethanol solution, the generation of aggregated precipitates increased. More preferably, in the cooling medium 37, 0.5% by weight to 1.0% by weight of the powder is mixed with the aqueous ethanol solution.
  • the water-soluble silicon compound contained in the cooling medium 37 is a slightly thick and transparent liquid.
  • the water-soluble silicon compound is a silicate.
  • a water-soluble silicon compound is produced by the following procedure.
  • High-purity silicon ore is calcined and gasified at a high temperature of about 1,600 degrees Celsius, and the gasified silicon component is recovered.
  • the recovered silicon becomes fine bead-shaped crystals.
  • the silicon crystals are heat-melted with a strong alkali or strong acid and liquefied.
  • an alkali e.g., sodium carbonate or sodium hydroxide
  • Sodium metasilicate is also known as the main component of hot springs. Since sodium metasilicate is a salt, it is solubilized. Liquefied hydrophilic silicon compounds are also soluble in water.
  • silicates including potassium silicate, calcium silicate or magnesium silicate
  • Silicates in detergents and soaps disperse dirt particles and prevent reattachment to clothing. It is widely known that silicate floats evenly in a liquid and moves.
  • Silica (SiO 2 ) is often used as an ion exchange substance, and hydrophilic silicon compounds also have electrical properties. Motility in a solution of a hydrophilic silicon compound is also evoked by electrical stimulation.
  • an inorganic silicon compound is preferable because its electrical characteristics are clear.
  • a water-soluble silicon compound In the cooling medium 37, 0.1% by weight to 1.0% by weight of a water-soluble silicon compound is mixed with the aqueous ethanol solution.
  • a water-soluble silicon compound when 0.1% by weight or more of a water-soluble silicon compound is mixed with an aqueous ethanol solution, it is suspended by mixing powders obtained by crushing the product obtained by thermally decomposing plant seeds. It was confirmed that it is effective in maintaining the state of. Further, according to the experiment, even if a water-soluble silicon compound exceeding 1.0% by weight was mixed with the ethanol aqueous solution, 1.0% by weight of the water-soluble silicon compound was mixed with the ethanol aqueous solution. There was no change in the maintenance of the case and suspension.
  • the cooling medium 37 0.1% by weight to 1.0% by weight of silicate is mixed with the aqueous ethanol solution. More preferably, in the cooling medium 37, 0.5% by weight to 1.0% by weight of the water-soluble silicon compound is mixed with the aqueous ethanol solution.
  • the water-soluble silicon compound contained in the cooling medium 37 disperses a powder obtained by crushing a product obtained by thermally decomposing plant seeds in an aqueous ethanol solution. Thereby, the water-soluble silicon compound suppresses the freezing of the cooling medium 37.
  • the freezing point of an aqueous ethanol solution having an ethanol concentration of 60% by weight is -45.4 degrees Celsius.
  • it is a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius in an aqueous ethanol solution having an ethanol concentration of 60% by weight, and is 0.5 with respect to the aqueous ethanol solution.
  • 0.5% by weight to 1.0% by weight of powder is mixed with 0.5% by weight to 1.0% by weight of a water-soluble silicon compound with respect to an aqueous ethanol solution, the liquid phase is maintained at -60 degrees Celsius.
  • FIG. 8 is a flowchart showing a procedure for manufacturing a frozen product.
  • the goods to be frozen may be tangible items other than real estate.
  • the goods to be frozen can be of biological origin in plants or animals.
  • the goods to be frozen can be food, cosmetics or medical products.
  • cosmetics can contain placenta (a component extracted from the placenta), collagen or amino acids.
  • medical products are medicines or medical devices obtained by processing cells such as human stem cells, organs, teeth, blood, cells or tissues, or biological products.
  • an aqueous ethanol solution is placed in a container.
  • the concentration of ethanol in the aqueous ethanol solution can be arbitrary.
  • the concentration of ethanol in the aqueous ethanol solution can be less than 60% by weight.
  • the concentration of ethanol in the aqueous ethanol solution can be any of 10% by weight to 90% by weight.
  • the concentration of ethanol in the aqueous ethanol solution is as high as 60% by weight or more, and when cooling to a temperature higher than -60 degrees Celsius, the concentration of ethanol in the aqueous ethanol solution is It is lower, less than 60% by weight.
  • the container in which the ethanol aqueous solution is placed in step S11 may be the container 36 or another container.
  • the container 36 is removed from the freezing chamber 31 of the freezer 1, and the ethanol aqueous solution is put into the container 36 outside the freezer 1.
  • step S12 the powder produced by thermally decomposing the seeds at 400 degrees Celsius or more and less than 500 degrees Celsius and pulverizing the seeds is mixed with the ethanol aqueous solution contained in the container.
  • the powder for example, it is a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius in an aqueous ethanol solution, and is 0.1% by weight to 1. 0% by weight of powder is mixed.
  • step S13 the water-soluble silicon compound is mixed with the ethanol aqueous solution contained in the container.
  • 0.1% by weight to 1.0% by weight of a water-soluble silicon compound is mixed with the aqueous ethanol solution.
  • step S14 an aqueous ethanol solution in which powder and a water-soluble silicon compound are mixed is placed in a container 36 in the freezer chamber 31 of the freezer 1.
  • the container 36 containing the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed is inside the freezer chamber 31 of the freezer 1. Returned to.
  • the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed is stored in the freezer. It is transferred to the container 36 in the freezing chamber 31 of 1.
  • step S15 the freezer 1 cools the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed to a temperature lower than zero degrees Celsius.
  • a temperature lower than zero degrees Celsius For example, when the concentration of ethanol in the aqueous ethanol solution is 60% by weight, the freezer 1 cools the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed to -60 degrees Celsius.
  • step S16 put the article to be frozen in a sealed container.
  • the article to be frozen is a food, cosmetic or medical article, it is a container formed of a plastic film or a metal foil or a multi-layered product thereof into a bag shape or other shape, and is heat-melted.
  • the article to be frozen is put in a sealed container (so-called pouch container) which is a container sealed by.
  • the sealed container is a container made of resin, metal, glass, or a combination thereof, which can be sealed so that the article to be frozen does not come into direct contact with the aqueous ethanol solution, and can withstand cooling to the temperature of the freezer chamber 31 of the freezer 1. It should be.
  • the article to be frozen may be in the form of a solid, a liquid, a sol or a gel.
  • step S17 the article placed in the sealed container is immersed in the cooled aqueous ethanol solution to freeze the article, and the procedure for manufacturing the frozen product is completed.
  • frozen products can be manufactured.
  • an aqueous ethanol solution By immersing in an aqueous ethanol solution, more heat is taken away in a shorter time, so that a frozen product can be produced faster.
  • the ethanol aqueous solution in which the powder and the water-soluble silicon compound are mixed does not solidify to a lower temperature as compared with the case of the ethanol aqueous solution alone, a frozen product can be produced even faster.
  • the ethanol aqueous solution in which the powder and the water-soluble silicon compound are mixed does not solidify to a lower temperature than the case of the ethanol aqueous solution alone, the deterioration of the frozen product can be further reduced, and more. It will be possible to store it for a long period of time.
  • aqueous ethanol solution with an ethanol concentration close to 60% by weight and less than 60% by weight of a non-dangerous substance is used, it is a non-dangerous substance and does not aggregate at -60 degrees Celsius, so that parasites are killed more safely. , The activity of the fungus can be suppressed.
  • the cooling medium 37 which is stored in the container 36 in the freezer 1 and cooled and used as a liquid for freezing the article by immersing the article, contains an aqueous ethanol solution and plant seeds at 400 ° C. or higher. It contains a powder obtained by crushing a product thermally decomposed at less than 500 degrees and a water-soluble silicon compound.
  • the hydrophilic powder becomes longer than the aqueous ethanol solution. Since the time-dispersed and the water-soluble silicon compound promotes the dispersion of the powder, the powder inhibits the coagulation of the aqueous ethanol solution and does not coagulate to a lower temperature than the case of the aqueous ethanol solution alone. , Will be able to be used at lower temperatures. This allows the article to be frozen faster.
  • a powder obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius and crushing the product and a water-soluble silicon compound are mixed in an aqueous ethanol solution.
  • the proportion of ethanol can be reduced and it can be used more safely. Since the powder and water-soluble silicon compound obtained by crushing the product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius are both harmless to the human body, it is assumed that they adhere to the immersed article. Can be handled more safely. In this way, it is possible to suppress coagulation at a lower temperature and freeze the article more safely and faster.
  • the powder may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution, and the water-soluble silicon compound may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution. ..
  • the hydrophilic powder can be dispersed in the aqueous ethanol solution for a long time, and the water-soluble silicon compound can promote the dispersion of the powder.
  • the powder When the powder is dispersed in an aqueous ethanol solution, the powder can be kept in a suspended state for 24 hours or more in a stationary state. By doing so, the powder can inhibit the coagulation of the aqueous ethanol solution for a longer period of time even when it is allowed to stand.
  • the powder can have a representative value of 10 ⁇ m or less, which indicates the center of the particle size distribution. By doing so, the powder can be easily dispersed and the coagulation of the aqueous ethanol solution can be inhibited.
  • the powder can contain 15% by weight to 19% by weight of potassium and 1% by weight to 3% by weight of phosphorus. By doing so, the powder becomes hydrophilic and can be dispersed in the ethanol aqueous solution for a long time to inhibit the coagulation of the ethanol aqueous solution.
  • the powder can generate a zeta potential of minus 0.5 mV in a pH 7 solution. By doing so, the powders repel each other and are easily dispersed, and the coagulation of the aqueous ethanol solution can be inhibited.
  • the powder can be made by crushing a product obtained by thermally decomposing seeds, which are beans. By doing so, it is possible to more reliably obtain a powder having desired properties, suppress coagulation at a lower temperature, and freeze the article more safely and faster.
  • the ethanol aqueous solution can contain less than 60% by weight of ethanol. By doing so, the water-soluble ethanol is treated as a non-dangerous substance in the Fire Service Act, and more cooling media 37 can be handled more easily.
  • the freezer 1 can store the cooling medium 37 in the internal container 36. By suppressing the solidification of the cooling medium 37 at a lower temperature, the article can be frozen more safely and faster.
  • a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 ° C. or higher and lower than 500 ° C. is mixed with an aqueous ethanol solution, and a water-soluble silicon compound is mixed with the aqueous ethanol solution.
  • Frozen product by cooling the aqueous ethanol solution mixed with the above to a temperature lower than 0 degrees Celsius in a liquid state, placing the article in a sealed container, and immersing the article in the sealed container in the cooled aqueous solution of ethanol to freeze it. Can be manufactured.

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Abstract

The present invention allows an article to be frozen more safely and faster at a lower temperature, while suppressing solidification. This method for producing a frozen article comprises: mixing into an aqueous ethanol solution a powder obtained by grinding a product from the thermal decomposition, at a temperature of 400°C or higher but lower than 500°C, of a plant seed; mixing a water-soluble silicon compound into the aqueous ethanol solution; cooling to a temperature of lower than 0°C the aqueous ethanol solution having the powder and the silicon compound mixed therein, while maintaining the aqueous ethanol solution in liquid form; and placing an article in a hermetic container and immersing into the cooled aqueous ethanol solution the article stored in the hermetic container, thereby freezing the article.

Description

冷却媒体、冷凍庫および冷凍品の製造方法Manufacturing method of cooling medium, freezer and frozen products
　本発明は冷却媒体、冷凍庫および冷凍品の製造方法に関し、特に、食品、化粧品または医療用の物品など冷凍する冷却媒体、冷凍庫および冷凍品の製造方法に関する。 The present invention relates to a method for manufacturing a cooling medium, a freezer and a frozen product, and more particularly to a method for manufacturing a cooling medium, a freezer and a frozen product for freezing such as food, cosmetics or medical articles.
　冷凍庫には、氷点下まで冷却した液体に対象物を浸けて冷凍させるブライン式冷凍庫がある。 The freezer has a brine-type freezer that freezes an object by immersing it in a liquid that has been cooled to below freezing point.
　従来、エチルアルコール、水、プロピレングリコールを含有して成る混合物を食品用のブラインとして使用することを特徴とするブライン組成物が提案されている（例えば、特許文献１参照）。 Conventionally, a brine composition has been proposed, characterized in that a mixture containing ethyl alcohol, water and propylene glycol is used as a brine for food (see, for example, Patent Document 1).
　また、炭素数が１乃至３の脂肪族アルコールを含有する水溶液に対し、その凍結温度を降下させるために、芳香族カルボン酸塩および亜硝酸塩からなる群から選ばれてなる少なくとも１つの化合物を配合したことを特徴とする冷却液組成物も提案されている（例えば、特許文献２参照）。 Further, in order to lower the freezing temperature of an aqueous solution containing an aliphatic alcohol having 1 to 3 carbon atoms, at least one compound selected from the group consisting of aromatic carboxylic acid salts and nitrites is blended. A coolant composition characterized by the above has also been proposed (see, for example, Patent Document 2).
特開平１０－１８３１０９号公報Japanese Unexamined Patent Publication No. 10-183109 特開平９－２２７８５９号公報Japanese Unexamined Patent Publication No. 9-227859
　しかしながら、特許文献１のブライン組成物や特許文献２の冷却液組成物では、安全性は考慮されているものの、摂氏マイナス４０度程度での使用が考えられている。 However, the brine composition of Patent Document 1 and the coolant composition of Patent Document 2 are considered to be used at about -40 degrees Celsius, although safety is taken into consideration.
　本発明は、このような状況に鑑みてなされたものであり、より低い温度で凝固を抑制して、より安全に、より速く物品を冷凍できるようにするものである。 The present invention has been made in view of such a situation, and suppresses coagulation at a lower temperature so that an article can be frozen more safely and faster.
　本発明の第１の側面の冷却媒体は、冷凍庫内の容器に溜められて冷却され、物品を浸けることにより物品を冷凍するための液状で用いられる冷却媒体であって、エタノール水溶液と、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と、水溶性のケイ素化合物とを含む。 The cooling medium according to the first aspect of the present invention is a cooling medium that is stored in a container in a freezer and cooled, and is used as a liquid for freezing the article by immersing the article in it. It contains a powder obtained by crushing a product obtained by thermally decomposing seeds at 400 ° C. or higher and lower than 500 ° C., and a water-soluble silicon compound.
　粉体は、エタノール水溶液に対して０．１重量％乃至１．０重量％とし、水溶性のケイ素化合物は、エタノール水溶液に対して０．１重量％乃至１．０重量％とすることができる。 The powder may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution, and the water-soluble silicon compound may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution. ..
　粉体は、エタノール水溶液に分散された場合、静置状態において２４時間以上懸濁の状態を維持するものとすることができる。 When the powder is dispersed in an aqueous ethanol solution, the powder can be kept in a suspended state for 24 hours or more in a stationary state.
　粉体は、粒子径の分布の中心を示す代表値が１０μｍ以下であるものとすることができる。 The powder can have a representative value of 10 μm or less, which indicates the center of the particle size distribution.
　粉体は、１５重量％乃至１９重量％のカリウムと１重量％乃至３重量％のリンとを含むものとすることができる。 The powder can contain 15% by weight to 19% by weight of potassium and 1% by weight to 3% by weight of phosphorus.
　粉体は、ｐＨ７の溶液中においてマイナス０．５ｍＶのゼータ電位を生じさせるものとすることができる。 The powder can generate a zeta potential of minus 0.5 mV in a pH 7 solution.
　粉体は、豆類である種子を熱分解した生成物を粉砕してなるものとすることができる。 The powder can be made by crushing a product obtained by thermally decomposing seeds, which are beans.
　エタノール水溶液は、６０重量％未満のエタノールを含むものとすることができる。 The ethanol aqueous solution can contain less than 60% by weight of ethanol.
　冷凍庫は、内部の容器に冷却媒体を溜めることができる。 The freezer can store the cooling medium in the internal container.
　本発明の第２の側面の冷凍品の製造方法は、エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体を混合し、エタノール水溶液に水溶性のケイ素化合物を混合し、粉体とケイ素化合物とが混合されたエタノール水溶液を液状のまま摂氏０度より低い温度に冷却し、物品を密封容器に入れ、密封容器に入れられた物品を冷却されたエタノール水溶液に浸けて冷凍させる。 In the method for producing a frozen product according to the second aspect of the present invention, a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 ° C. or higher and lower than 500 ° C. is mixed with an aqueous ethanol solution to prepare an aqueous ethanol solution. A water-soluble silicon compound is mixed, and the ethanol aqueous solution in which the powder and the silicon compound are mixed is cooled to a temperature lower than 0 ° C. in a liquid state, the article is placed in a sealed container, and the article placed in the sealed container is placed. Immerse in a cooled aqueous solution of ethanol and freeze.
　エタノール水溶液に対して０．１重量％乃至１．０重量％の粉体を混合し、エタノール水溶液に対して０．１重量％乃至１．０重量％の水溶性のケイ素化合物を混合することができる。 It is possible to mix 0.1% by weight to 1.0% by weight of powder with an aqueous ethanol solution and 0.1% by weight to 1.0% by weight of a water-soluble silicon compound with an aqueous ethanol solution. can.
　以上のように、本発明によれば、より低い温度で凝固を抑制して、より安全に、より速く物品を冷凍できる。 As described above, according to the present invention, solidification can be suppressed at a lower temperature, and the article can be frozen more safely and faster.
本発明の一実施の形態の冷凍庫の外観を説明する図である。It is a figure explaining the appearance of the freezer of one Embodiment of this invention. 冷凍庫１の断面図である。It is sectional drawing of the freezer 1. 粒径が５μｍ程度の粉体を示す図である。It is a figure which shows the powder which the particle size is about 5 μm. 粉体の成分分析の結果の例を示す図である。It is a figure which shows the example of the result of the component analysis of a powder. 粉体の粒度分布を示す図である。It is a figure which shows the particle size distribution of a powder. 植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に混合したときの状態を示す図である。It is a figure which shows the state when the powder which is made by crushing the product which pyrolyzed the seed of a plant is mixed with the aqueous ethanol solution. 静置状態で２４時間経過した場合の粉体が混合されたエタノール水溶液の状態を示す図である。It is a figure which shows the state of the ethanol aqueous solution mixed with the powder when 24 hours have passed in the stationary state. 冷凍品の製造の手順を示すフローチャートである。It is a flowchart which shows the procedure of manufacturing a frozen product.
　以下、図１乃至図８を参照して、本発明の実施の形態を説明する。 Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 8.
　図１は、本発明の一実施の形態の冷凍庫の外観を説明する図である。冷凍庫１は、冷凍庫の一例であり、外形が概ね直方体状に形成されている一体型冷凍庫である。冷凍庫１は、圧縮機、凝縮器、膨張弁および蒸発器などを内蔵し、後述する冷凍室の内壁に冷却器が埋設され、摂氏零度より低い温度まで冷凍室を冷却する。冷凍庫１は、圧縮機、凝縮器、膨張弁および蒸発器などを内蔵し、内部に冷凍室が設けられている本体１１と、本体１１に対してヒンジ（図示せず）を介して開閉自在に設けられている扉１２と、冷凍室内の温度を調節するための温度調節器１３とを含み構成されている。 FIG. 1 is a diagram illustrating the appearance of the freezer according to the embodiment of the present invention. The freezer 1 is an example of a freezer, and is an integrated freezer having a substantially rectangular parallelepiped outer shape. The freezer 1 incorporates a compressor, a condenser, an expansion valve, an evaporator, and the like, and a cooler is embedded in the inner wall of the freezer chamber, which will be described later, to cool the freezer chamber to a temperature lower than zero degrees Celsius. The freezer 1 has a built-in compressor, condenser, expansion valve, evaporator, etc., and can be opened and closed freely with respect to the main body 11 having a freezing chamber inside and the main body 11 via a hinge (not shown). It includes a door 12 provided and a temperature controller 13 for adjusting the temperature in the freezing chamber.
　なお、図１において、３次元空間（直交座標空間）を表すＸ軸、Ｙ軸およびＺ軸からなる座標軸で示される方向のうち、図１中の右上と左下とを結ぶ方向はＸ軸方向を示し、図１中の右下と左上とを結ぶ方向はＹ軸方向を示し、図１中の上下方向はＺ軸方向を示す。 In FIG. 1, among the directions indicated by the X-axis, Y-axis, and Z-axis representing the three-dimensional space (Cartesian coordinate space), the direction connecting the upper right and the lower left in FIG. 1 is the X-axis direction. The direction connecting the lower right and the upper left in FIG. 1 indicates the Y-axis direction, and the vertical direction in FIG. 1 indicates the Z-axis direction.
　図２は、Ｘ軸およびＺ軸で規定される平面であって、図１のAA’線で示される位置に沿った平面での断面を示す冷凍庫１の断面図である。冷凍庫１の内側には、冷却される空間である冷凍室３１が形成されている。冷凍室３１の下側、すなわち、本体１１側は、鋼板からなる冷却器３２で囲われている。冷却器３２の面のうち、冷凍室３１側の面に対向する面には、圧縮機、凝縮器および膨張弁などからなるコンデンシングユニット３３に配管で接続されている熱交換器が設けられている。熱交換器は、冷却器３２から吸熱して、コンデンシングユニット３３の凝縮器は、排熱する。これにより、冷凍室３１が冷却される。 FIG. 2 is a cross-sectional view of the freezer 1 showing a cross section in a plane defined by the X-axis and the Z-axis and along the position indicated by the AA'line in FIG. Inside the freezer 1, a freezing chamber 31, which is a space for cooling, is formed. The lower side of the freezing chamber 31, that is, the main body 11 side is surrounded by a cooler 32 made of a steel plate. A heat exchanger connected to a condensing unit 33 including a compressor, a condenser, an expansion valve, etc. by a pipe is provided on the surface of the cooler 32 facing the surface on the freezing chamber 31 side. There is. The heat exchanger absorbs heat from the cooler 32, and the condenser of the condensing unit 33 exhausts heat. As a result, the freezing chamber 31 is cooled.
　冷却器３２の外側は、発泡ポリウレタン樹脂または真空パネルなどからなる断熱材３４で覆われている。また、扉１２には、発泡ポリウレタン樹脂または真空パネルなどからなる断熱材３５が詰められている。すなわち、冷凍室３１の全体は、断熱材３４および断熱材３５で囲われている。 The outside of the cooler 32 is covered with a heat insulating material 34 made of polyurethane foam resin, a vacuum panel, or the like. Further, the door 12 is filled with a heat insulating material 35 made of a foamed polyurethane resin, a vacuum panel, or the like. That is, the entire freezing chamber 31 is surrounded by the heat insulating material 34 and the heat insulating material 35.
　冷凍庫１の冷凍室３１内には、容器３６が設けられている。容器３６は、ステンレススチールやガルバナイズ鋼板など、伝熱性の高い材料で形成されている。容器３６は、内部に液状の冷却媒体３７が溜められている。例えば、容器３６は、槽状に形成されている。なお、容器３６は、液状の冷却媒体３７を溜めることが出来ればよく、半球状のボール状としても、蓋を設けたりしても良い。例えば、容器３６は、冷凍庫１の冷凍室３１から取り外し可能とされている。 A container 36 is provided in the freezing chamber 31 of the freezer 1. The container 36 is made of a highly heat-conducting material such as stainless steel or a galvanized steel plate. A liquid cooling medium 37 is stored in the container 36. For example, the container 36 is formed in a tank shape. The container 36 may be in the shape of a hemispherical ball or may be provided with a lid, as long as it can store the liquid cooling medium 37. For example, the container 36 is removable from the freezing chamber 31 of the freezer 1.
　なお、冷凍庫１は、一体型冷凍庫に限らず、所望の温度まで冷却できるものであればよく、定置式冷凍ユニット、コンデンシングユニットと別置型ショーケース若しくは冷凍倉庫とからなるものであっても、縦型または横型の業界用冷凍庫であってもよい。また、冷凍庫１は、いずれの冷却方式でもよく、往復動式（レシプロ式）若しくは回転式の容量圧縮式、遠心式（ターボ式）、吸収式、空気冷凍サイクルを利用したターボ型、ペルチェ効果を利用した電子冷凍機または磁気冷凍機とすることができる。 The freezer 1 is not limited to the integrated freezer, and may be any one that can be cooled to a desired temperature, and may be composed of a stationary freezer unit, a condensining unit, and a separate showcase or a freezer warehouse. It may be a vertical or horizontal industrial freezer. Further, the freezer 1 may be of any cooling method, and has a reciprocating type (reciprocal type) or a rotary capacity compression type, a centrifugal type (turbo type), an absorption type, a turbo type using an air refrigeration cycle, and a Pelche effect. It can be the electronic refrigerator or magnetic refrigerator used.
　次に、冷却媒体３７の詳細について説明する。冷却媒体３７は、冷凍庫１内の容器３６に溜められて冷却され、物品を浸けることにより物品を冷凍するために液状で用いられる。冷却媒体３７は、エタノール水溶液と、植物の種子を熱分解した生成物を粉砕してなる粉体と、水溶性のケイ素化合物とを含む。 Next, the details of the cooling medium 37 will be described. The cooling medium 37 is stored in a container 36 in the freezer 1 and cooled, and is used in a liquid state for freezing the article by immersing the article. The cooling medium 37 contains an aqueous ethanol solution, a powder obtained by crushing a product obtained by thermally decomposing plant seeds, and a water-soluble silicon compound.
　エタノール水溶液は、エタノール（エチルアルコール）と水とを所定の割合で混合したものである。エタノールは、様々な有機物質を溶解でき、１価アルコール類の中では比較的毒性が低い。また、エタノールは、水と自由な割合で混和することができる。エタノール水溶液において、エタノールの濃度は、任意の値とすることができ、例えば、１０重量％乃至９０重量％とすることができる。 The ethanol aqueous solution is a mixture of ethanol (ethyl alcohol) and water in a predetermined ratio. Ethanol can dissolve various organic substances and is relatively less toxic among monohydric alcohols. In addition, ethanol can be miscible with water in any proportion. In the aqueous ethanol solution, the concentration of ethanol can be any value, for example, 10% by weight to 90% by weight.
　例えば、エタノールの濃度が６０重量％の場合、エタノール水溶液単独の凝固点は、摂氏マイナス４５．４度である。 For example, when the concentration of ethanol is 60% by weight, the freezing point of the aqueous ethanol solution alone is -45.4 degrees Celsius.
　また、エタノールの濃度が６０重量％未満の場合、エタノール水溶は、消防法において、非危険物として扱われる。 If the concentration of ethanol is less than 60% by weight, water-soluble ethanol is treated as a non-dangerous substance under the Fire Service Act.
　次に、冷却媒体３７に含まれる粉体の詳細について説明する。 Next, the details of the powder contained in the cooling medium 37 will be described.
　エタノール水溶液に混合される粉体は、植物の種子を熱分解した生成物を粉砕してなる。例えば、植物の種子は、小豆、大豆、いんげん豆、エンドウ豆、ささげ、そらまめ、ひよこ豆、レンズ豆または落花生の種子などの豆類である。植物の種子は、半密閉の電気炉で摂氏４００度以上５００度未満の温度で熱分解される。植物の種子が熱分解されて得られた生成物は、ボールミルなどの粉砕機で、粒子径の分布の中心を示す代表値が１０μｍ以下である粉体に粉砕される。 The powder mixed with the aqueous ethanol solution is made by crushing the product of pyrolysis of plant seeds. For example, plant seeds are legumes such as adzuki beans, soybeans, green beans, peas, cowpeas, broad beans, chick beans, lentils or peanut seeds. Plant seeds are pyrolyzed in a semi-enclosed electric furnace at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius. The product obtained by thermally decomposing plant seeds is pulverized by a pulverizer such as a ball mill into a powder having a representative value of 10 μm or less, which indicates the center of particle size distribution.
　ここで、半密閉とは、大気雰囲気よりも酸素分圧が減じられている状態をいう。例えば、半密閉は、炭焼き窯のように、焼成空間内の雰囲気と外気との置換が抑制されるように、焼成空間と外部とを隙間や小孔で連通するようにした状態をいう。このようにすることで、植物の種子は、酸化または燃焼が抑制された状態で加熱され、熱分解される。例えば、植物の種子をアルミナ容器に収容して、電気炉で加熱することで、植物の種子を熱分解した生成物を得ることができる。 Here, semi-sealed means a state in which the oxygen partial pressure is reduced compared to the atmospheric atmosphere. For example, semi-sealing refers to a state in which the firing space and the outside are communicated with each other through gaps or small holes so that replacement of the atmosphere inside the firing space with the outside air is suppressed, as in a charcoal kiln. By doing so, the seeds of the plant are heated and thermally decomposed in a state where oxidation or combustion is suppressed. For example, by housing the plant seeds in an alumina container and heating them in an electric furnace, a product obtained by thermally decomposing the plant seeds can be obtained.
　植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物は、中低温での熱分解処理のため、柔らかく、極めて容易に粉砕できる。これに対して、備長炭は、摂氏１，０００度近くの高温で焼成処理が行われるので、金属並みの硬度を有する。 The product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius is soft and can be crushed extremely easily because of the thermal decomposition treatment at medium and low temperatures. On the other hand, Bincho charcoal has a hardness comparable to that of metal because it is fired at a high temperature of about 1,000 degrees Celsius.
　例えば、植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物を、アルミナボールと共にボールミルポットに入れて、ボールミルポットを回転させることで粉砕する。例えば、粉砕して得られた粉体は、所定のメッシュのふるいにかけられる。 For example, a product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius is placed in a ball mill pot together with alumina balls and crushed by rotating the ball mill pot. For example, the powder obtained by grinding is sieved by a predetermined mesh.
　図３は、走査型電子顕微鏡を用いて１０，０００倍で撮影した、粒径が５μｍ程度の粉体を示す図である。粉体の外形には角がなく、容易に粉砕されることがわかる。また、粉体には、微細孔が生じていない。 FIG. 3 is a diagram showing a powder having a particle size of about 5 μm, taken at 10,000 times using a scanning electron microscope. It can be seen that the outer shape of the powder has no corners and is easily crushed. Further, the powder does not have fine pores.
　図４は、粉体の成分分析の結果の例を示す図である。図４に示される粉体に含まれる元素の割合は、ＣＨＮ元素分析（Elemental Analysis(Carbon, Hydrogen, Nitrogen)）および蛍光X線分析により求められたものである。図４に示される例において、小豆である植物の種子を熱分解した生成物を粉砕してなる粉体には、６６．５重量％の炭素、１７．１重量％のカリウム、６．１重量％の窒素、４．２重量％の水素、２．７８重量％のリン、１．４重量％のカルシウム、０．８重量％のマグネシウム、０．５重量％の硫黄、０．２６重量％の鉄、０．０７重量％の亜鉛、０．０５重量％のマンガン、０．０３重量％のケイ素、０．０２重量％のアルミニウムおよび０．０１重量％の銅が含まれている。 FIG. 4 is a diagram showing an example of the result of component analysis of powder. The ratio of the elements contained in the powder shown in FIG. 4 was determined by CHN elemental analysis (Elemental Analysis (Carbon, Hydrogen, Nitrogen)) and fluorescent X-ray analysis. In the example shown in FIG. 4, the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant, which is a small bean, contains 66.5% by weight of carbon, 17.1% by weight of potassium, and 6.1% by weight. % Nitrogen, 4.2% by weight hydrogen, 2.78% by weight phosphorus, 1.4% by weight calcium, 0.8% by weight magnesium, 0.5% by weight sulfur, 0.26% by weight It contains iron, 0.07% by weight zinc, 0.05% by weight manganese, 0.03% by weight silicon, 0.02% by weight aluminum and 0.01% by weight copper.
　植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物には、カリウムおよびリンが含まれ、これにより親水性が生じる。ここで、カリウムは、アルカリ金属である。また、植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物には、マグネシウムが含まれている。マグネシウムは、アルカリ水を生成させる。 The product of pyrolyzing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius contains potassium and phosphorus, which results in hydrophilicity. Here, potassium is an alkali metal. In addition, magnesium is contained in the product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius. Magnesium produces alkaline water.
　小豆、大豆、エンドウ豆、ひよこ豆または落花生の種子などの豆類である植物の種子を熱分解した生成物を粉砕してなる粉体には、１５重量％乃至１９重量％のカリウムと１重量％乃至３重量％のリンとが含まれる。また、豆類を熱分解した生成物は、比較的容易に粉砕することができ、粒子径の分布の中心の値が１０μｍ以下である粉体を容易に得ることができる。 15% to 19% by weight of potassium and 1% by weight are contained in the powder obtained by crushing the product obtained by pyrolyzing the seeds of plants such as red beans, soybeans, peas, chickpeas or peanut seeds. It contains from 3% by weight of phosphorus. In addition, the product obtained by thermally decomposing beans can be pulverized relatively easily, and a powder having a value at the center of the particle size distribution of 10 μm or less can be easily obtained.
　これに対して、摂氏５００度以上で熱分解した場合、炭素以外の元素の含有比率が下がり、摂氏８００度以上で熱分解した場合、炭素の含有比率は、９５重量％を超える。熱分解の温度が高く、炭化が進みすぎると、焼成物は水溶性を失う。 On the other hand, when pyrolyzed at 500 degrees Celsius or higher, the content ratio of elements other than carbon decreases, and when pyrolyzed at 800 degrees Celsius or higher, the carbon content ratio exceeds 95% by weight. If the temperature of pyrolysis is high and carbonization progresses too much, the fired product loses its water solubility.
　また、一般的に、電気性を帯びた粒子（微粒子）が溶液の中で移動する場合、微弱な電流が発生する。植物の種子を熱分解した生成物を粉砕してなる粉体は、ｐＨ７の溶液中においてマイナス０．５ｍＶのゼータ電位を生じさせる。従って、植物の種子を熱分解した生成物を粉砕してなる粉体は、タンパク質などのプラス電位を持つ物質と結合するなどの独特の化学反応を生じさせる。また、植物の種子を熱分解した生成物を粉砕してなる粉体は、ｐＨ７の溶液中においてマイナス０．５ｍＶのゼータ電位を生じさせるので、互いに反発しあい、分散しやすくなる。 Also, in general, when electrically charged particles (fine particles) move in a solution, a weak electric current is generated. The powder obtained by grinding the product of pyrolysis of plant seeds produces a zeta potential of minus 0.5 mV in a solution at pH 7. Therefore, the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant causes a unique chemical reaction such as binding to a substance having a positive potential such as a protein. Further, the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant generates a zeta potential of minus 0.5 mV in a solution of pH 7, so that they repel each other and easily disperse.
　さらに、小豆である植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物を、ボールミルなどの粉砕機で粉砕して得られた粉体の粒度分布を測定した。なお、粉体の粒度分布の測定は、粒子群にレーザ光を照射し、そこから発せられる回折・散乱光の強度分布パターンから計算によって粒度分布を求めるレーザ回折式粒子径分布測定装置を用いた。この場合、レーザ回折式粒子径分布測定装置の測定範囲は、０．０５μｍから３，０００μｍまでである。測定回数は４回である。 Furthermore, the particle size distribution of the powder obtained by pyrolyzing the seeds of a plant, which is a small bean, at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius by crushing it with a crusher such as a ball mill was measured. The particle size distribution of the powder was measured by using a laser diffraction type particle size distribution measuring device that irradiates the particle group with laser light and obtains the particle size distribution by calculation from the intensity distribution pattern of the diffraction / scattered light emitted from the particle group. .. In this case, the measurement range of the laser diffraction type particle size distribution measuring device is from 0.05 μm to 3,000 μm. The number of measurements is four.
　図５は、体積相対粒度分布および個数相対粒度分布により、測定された粉体の粒度分布を示す図である。図５の横軸は、粒子径（μｍ）を対数で示し、縦軸は、相対粒子量（％）を示す。平均粒径（平均値）は、７．４μｍであり、最頻値（モード）は、８．５μｍである。中央値（メディアン）は、８．４９１μｍである。平均偏差は、０．３７３である。平均値、最頻値および中央値は、それぞれ、粒子径の分布の中心を示す代表値の一例である。 FIG. 5 is a diagram showing the particle size distribution of the powder measured by the volume relative particle size distribution and the number relative particle size distribution. The horizontal axis of FIG. 5 indicates the particle size (μm) in a logarithm, and the vertical axis indicates the relative particle amount (%). The average particle size (average value) is 7.4 μm, and the mode is 8.5 μm. The median is 8.491 μm. The average deviation is 0.373. The average value, mode value, and median value are examples of representative values indicating the center of the particle size distribution, respectively.
　このように、植物の種子を熱分解した生成物を粉砕してなる粉体は、粒子径の分布の中心を示す代表値が１０μｍ以下となるまで粉砕される。なお、植物の種子を熱分解した生成物を粉砕してなる粉体は、粒子径の分布の中心を示す代表値が３μｍ以上となるまで粉砕することができる。 As described above, the powder obtained by crushing the product obtained by thermally decomposing the seeds of the plant is crushed until the representative value indicating the center of the particle size distribution becomes 10 μm or less. The powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant can be crushed until the representative value indicating the center of the particle size distribution becomes 3 μm or more.
　次に、植物の種子を熱分解した生成物を粉砕してなる粉体の親水性について説明する。図６は、植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に混合したときの状態を示す図である。植物の種子を熱分解した生成物を粉砕してなる粉体は、高い濡れ性を有し、速やかにエタノール水溶液に沈降する。 Next, the hydrophilicity of the powder obtained by crushing the product obtained by thermally decomposing the seeds of the plant will be described. FIG. 6 is a diagram showing a state when a powder obtained by crushing a product obtained by thermally decomposing plant seeds is mixed with an aqueous ethanol solution. The powder obtained by crushing the product obtained by thermally decomposing plant seeds has high wettability and quickly precipitates in an aqueous ethanol solution.
　エタノール水溶液に対して、植物の種子を熱分解した生成物を粉砕してなる粉体を１重量％混合すると懸濁液となり、墨汁状の液体となる。 When 1% by weight of powder obtained by crushing the product obtained by thermally decomposing plant seeds is mixed with an aqueous ethanol solution, it becomes a suspension and becomes a liquid like ink.
　これに対して、広葉樹木を材料に摂氏８００度以上の高温で焼成される一般的な炭を粉砕して生成された粒子は、強い疎水性を示し、濡れ性も低いため、エタノール水溶液に混合すると、表面にしばらく浮遊してから沈降する。なお、一般的な炭を粉砕して粒子を生成しても、微粒化が困難であり、その粒径はおおむね２０μｍとなる。 On the other hand, particles produced by crushing general charcoal that is fired at a high temperature of 800 degrees Celsius or higher using hardwood as a material show strong hydrophobicity and low wettability, so they are mixed with an aqueous ethanol solution. Then, it floats on the surface for a while and then sinks. Even if general charcoal is crushed to generate particles, it is difficult to atomize the particles, and the particle size is about 20 μm.
　エタノール水溶液に対して、一般的な炭を粉砕してなる粉体を１重量％混合すると直後は懸濁液となり、墨汁状の液体となる。 When 1% by weight of powder made by crushing general charcoal is mixed with an aqueous ethanol solution, it immediately becomes a suspension and becomes a liquid like ink.
　植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に混合して分散させ、静置状態で２４時間以上経過しても懸濁の状態が維持される。図７は、静置状態で２４時間経過した場合の粉体が混合されたエタノール水溶液の状態を示す図である。図７中の左側は、植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に分散させて静置状態で２４時間経過した状態を示す。図７中の右側は、一般的な炭を粉砕してなる粉体をエタノール水溶液に分散させて静置状態で２４時間経過した状態を示す。 The powder obtained by crushing the product obtained by thermally decomposing plant seeds is mixed with an aqueous ethanol solution and dispersed, and the suspended state is maintained even after 24 hours or more have passed in a stationary state. FIG. 7 is a diagram showing a state of an ethanol aqueous solution mixed with powder when 24 hours have passed in a stationary state. The left side in FIG. 7 shows a state in which a powder obtained by crushing a product obtained by thermally decomposing plant seeds is dispersed in an aqueous ethanol solution and left standing for 24 hours. The right side in FIG. 7 shows a state in which a powder made by crushing general charcoal is dispersed in an aqueous ethanol solution and left standing for 24 hours.
　一般的な炭を粉砕してなる粉体をエタノール水溶液に分散させて静置状態で２４時間経過すると、粒子が沈殿してしまい、上澄みは透明になる。これに対して、植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に分散させると、静置状態で２４時間経過しても、墨汁状を維持し、懸濁の状態が維持される。植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液に分散させると、１週間程度経過しても、容器の底に若干の凝集沈殿物が発生するが、懸濁の状態が維持される。 When powder made by crushing general charcoal was dispersed in an aqueous ethanol solution and left to stand for 24 hours, the particles settled and the supernatant became transparent. On the other hand, when the powder obtained by crushing the product obtained by thermally decomposing the seeds of a plant is dispersed in an aqueous ethanol solution, it maintains the ink-like state even after 24 hours in a stationary state and is in a suspended state. Is maintained. When the powder obtained by crushing the product obtained by thermally decomposing the plant seeds is dispersed in an aqueous ethanol solution, some aggregated precipitates are formed on the bottom of the container even after about one week, but they are in a suspended state. Is maintained.
　冷却媒体３７において、エタノール水溶液に対して０．１重量％乃至１．０重量％の粉体が混合させられる。実験によれば、エタノール水溶液に対して０．１重量％以上の粉体が混合させられると、冷却媒体３７の凝固点の降下が認められた。また、実験によれば、エタノール水溶液に対して１．０重量％を超える粉体が混合させられると、凝集沈殿物の発生が増えることが確認された。より好ましくは、冷却媒体３７において、エタノール水溶液に対して０．５重量％乃至１．０重量％の粉体が混合させられる。 In the cooling medium 37, 0.1% by weight to 1.0% by weight of powder is mixed with the aqueous ethanol solution. According to the experiment, when 0.1% by weight or more of the powder was mixed with the aqueous ethanol solution, a decrease in the freezing point of the cooling medium 37 was observed. Further, according to the experiment, it was confirmed that when a powder exceeding 1.0% by weight was mixed with the aqueous ethanol solution, the generation of aggregated precipitates increased. More preferably, in the cooling medium 37, 0.5% by weight to 1.0% by weight of the powder is mixed with the aqueous ethanol solution.
　また、植物の種子を摂氏４００度以上５００度未満の温度で熱分解した生成物は、人体に無害であることが確認できた。 It was also confirmed that the product obtained by thermally decomposing plant seeds at a temperature of 400 degrees Celsius or more and less than 500 degrees Celsius is harmless to the human body.
　次に、冷却媒体３７に含まれる水溶性のケイ素化合物について説明する。水溶性のケイ素化合物は、ややとろみを有する透明な液体である。例えば、水溶性のケイ素化合物は、ケイ酸塩である。 Next, the water-soluble silicon compound contained in the cooling medium 37 will be described. The water-soluble silicon compound is a slightly thick and transparent liquid. For example, the water-soluble silicon compound is a silicate.
　例えば、水溶性のケイ素化合物は、次のような手順で生成される。ケイ素の純度の高い鉱石が、摂氏１，６００度程度の高温で焼成されてガス化させられ、ガス化したケイ素成分が回収される。この回収されたケイ素は、常温では、細かいビーズ状の結晶となる。このケイ素の結晶が、強アルカリまたは強酸で加熱融解処理され、液化させられる。例えば、アルカリ（例えば、炭酸ナトリウムまたは水酸化ナトリウム）で処理されたケイ素は、ケイ酸ナトリウム（Na2SiO3）（メタケイ酸ナトリウム）すなわち塩となり、水溶性（水に可溶性）となる。 For example, a water-soluble silicon compound is produced by the following procedure. High-purity silicon ore is calcined and gasified at a high temperature of about 1,600 degrees Celsius, and the gasified silicon component is recovered. At room temperature, the recovered silicon becomes fine bead-shaped crystals. The silicon crystals are heat-melted with a strong alkali or strong acid and liquefied. For example, an alkali (e.g., sodium carbonate or sodium hydroxide) silicon treated with the sodium silicate (Na 2 SiO 3) (sodium metasilicate) That becomes salt, a water-soluble (soluble in water).
　また、稲の籾殻を燃焼させて、その灰を強アルカリ処理し、液化したケイ素化合物を抽出することにより水溶性のケイ素化合物を得ることもできる。 It is also possible to obtain a water-soluble silicon compound by burning rice husks, treating the ash with a strong alkali, and extracting a liquefied silicon compound.
　メタケイ酸ナトリウムは、温泉の主要成分としても知られている。メタケイ酸ナトリウムは、塩であるため水溶化する。液化親水性ケイ素化合物も水に可溶性である。 Sodium metasilicate is also known as the main component of hot springs. Since sodium metasilicate is a salt, it is solubilized. Liquefied hydrophilic silicon compounds are also soluble in water.
　一般的なケイ酸塩（ケイ酸カリウム、ケイ酸カルシウムまたはケイ酸マグネシウムなどが含まれる）は、洗剤や石鹸に配合される。洗剤や石鹸に配合されるケイ酸塩は、汚れ粒子を分散させ、衣類への再付着を抑制する。ケイ酸塩は、液体中をまんべんなく浮遊し運動することが広く知られている。 General silicates (including potassium silicate, calcium silicate or magnesium silicate) are added to detergents and soaps. Silicates in detergents and soaps disperse dirt particles and prevent reattachment to clothing. It is widely known that silicate floats evenly in a liquid and moves.
　シリカ（SiO2）は、イオン交換物質として多用されており、親水性ケイ素化合物も電気的な特性を有する。親水性ケイ素化合物の溶液中の運動性も電気的刺激により惹起される。 Silica (SiO 2 ) is often used as an ion exchange substance, and hydrophilic silicon compounds also have electrical properties. Motility in a solution of a hydrophilic silicon compound is also evoked by electrical stimulation.
　なお、冷却媒体３７に含まれる水溶性のケイ素化合物としては、電気的な特性が明らかなので、無機ケイ素化合物が、好ましい。 As the water-soluble silicon compound contained in the cooling medium 37, an inorganic silicon compound is preferable because its electrical characteristics are clear.
　冷却媒体３７において、エタノール水溶液に対して０．１重量％乃至１．０重量％の水溶性のケイ素化合物が混合させられる。実験によれば、エタノール水溶液に対して０．１重量％以上の水溶性のケイ素化合物が混合させられると、植物の種子を熱分解した生成物を粉砕してなる粉体の混合による、懸濁の状態の維持に効果的であることが確認できた。また、実験によれば、エタノール水溶液に対して１．０重量％を超える水溶性のケイ素化合物を混合させても、エタノール水溶液に対して１．０重量％の水溶性のケイ素化合物を混合させた場合と懸濁の状態の維持に変化が見られなかった。例えば、冷却媒体３７において、エタノール水溶液に対して０．１重量％乃至１．０重量％のケイ酸塩が混合させられる。より好ましくは、冷却媒体３７において、エタノール水溶液に対して０．５重量％乃至１．０重量％の水溶性のケイ素化合物が混合させられる。 In the cooling medium 37, 0.1% by weight to 1.0% by weight of a water-soluble silicon compound is mixed with the aqueous ethanol solution. According to experiments, when 0.1% by weight or more of a water-soluble silicon compound is mixed with an aqueous ethanol solution, it is suspended by mixing powders obtained by crushing the product obtained by thermally decomposing plant seeds. It was confirmed that it is effective in maintaining the state of. Further, according to the experiment, even if a water-soluble silicon compound exceeding 1.0% by weight was mixed with the ethanol aqueous solution, 1.0% by weight of the water-soluble silicon compound was mixed with the ethanol aqueous solution. There was no change in the maintenance of the case and suspension. For example, in the cooling medium 37, 0.1% by weight to 1.0% by weight of silicate is mixed with the aqueous ethanol solution. More preferably, in the cooling medium 37, 0.5% by weight to 1.0% by weight of the water-soluble silicon compound is mixed with the aqueous ethanol solution.
　冷却媒体３７に含まれる水溶性のケイ素化合物は、植物の種子を熱分解した生成物を粉砕してなる粉体をエタノール水溶液中に分散させる。これにより、水溶性のケイ素化合物は、冷却媒体３７の凍結を抑制する。 The water-soluble silicon compound contained in the cooling medium 37 disperses a powder obtained by crushing a product obtained by thermally decomposing plant seeds in an aqueous ethanol solution. Thereby, the water-soluble silicon compound suppresses the freezing of the cooling medium 37.
　言い換えれば、エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と、水溶性のケイ素化合物とを混合すると、凝固点が下がる。 In other words, when a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius in an aqueous ethanol solution and a water-soluble silicon compound are mixed, the freezing point is lowered.
　エタノールの濃度が６０重量％のエタノール水溶液の凝固点は、摂氏マイナス４５．４度である。例えば、エタノールの濃度が６０重量％のエタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体であって、エタノール水溶液に対して０．５重量％乃至１．０重量％の粉体と、エタノール水溶液に対して０．５重量％乃至１．０重量％の水溶性のケイ素化合物とを混合すると、摂氏マイナス６０度で液相を維持し、液状の冷却媒体３７として摂氏マイナス６０度で実用できる。 The freezing point of an aqueous ethanol solution having an ethanol concentration of 60% by weight is -45.4 degrees Celsius. For example, it is a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius in an aqueous ethanol solution having an ethanol concentration of 60% by weight, and is 0.5 with respect to the aqueous ethanol solution. When 0.5% by weight to 1.0% by weight of powder is mixed with 0.5% by weight to 1.0% by weight of a water-soluble silicon compound with respect to an aqueous ethanol solution, the liquid phase is maintained at -60 degrees Celsius. , Can be put into practical use as a liquid cooling medium 37 at -60 degrees Celsius.
　図８は、冷凍品の製造の手順を示すフローチャートである。ここで、冷凍する物品は、不動産以外の有体物であればよい。冷凍する物品は、植物または動物の生物由来の物とすることができる。例えば、冷凍する物品は、食品、化粧品または医療用の物とすることができる。例えば、化粧品は、プラセンタ（胎盤から抽出した成分）、コラーゲンまたはアミノ酸を含んだものとすることができる。例えば、医療用の物は、ヒト幹細胞などの細胞、臓器、歯、血液、細胞若しくは組織を加工した医薬品若しくは医療機器、または生物由来製品などである。 FIG. 8 is a flowchart showing a procedure for manufacturing a frozen product. Here, the goods to be frozen may be tangible items other than real estate. The goods to be frozen can be of biological origin in plants or animals. For example, the goods to be frozen can be food, cosmetics or medical products. For example, cosmetics can contain placenta (a component extracted from the placenta), collagen or amino acids. For example, medical products are medicines or medical devices obtained by processing cells such as human stem cells, organs, teeth, blood, cells or tissues, or biological products.
　ステップＳ１１において、エタノール水溶液が容器に入れられる。ここで、エタノール水溶液のエタノールの濃度は、任意とすることができる。例えば、エタノール水溶液のエタノールの濃度は、６０重量％未満とすることができる。さらに、例えば、エタノール水溶液のエタノールの濃度は、１０重量％乃至９０重量％のいずれかとすることができる。摂氏マイナス６０度より低い温度まで冷却する場合、エタノール水溶液のエタノールの濃度は、６０重量％以上と、より高くされ、摂氏マイナス６０度より高い温度まで冷却する場合、エタノール水溶液のエタノールの濃度は、６０重量％未満と、より低くされる。 In step S11, an aqueous ethanol solution is placed in a container. Here, the concentration of ethanol in the aqueous ethanol solution can be arbitrary. For example, the concentration of ethanol in the aqueous ethanol solution can be less than 60% by weight. Further, for example, the concentration of ethanol in the aqueous ethanol solution can be any of 10% by weight to 90% by weight. When cooling to a temperature lower than -60 degrees Celsius, the concentration of ethanol in the aqueous ethanol solution is as high as 60% by weight or more, and when cooling to a temperature higher than -60 degrees Celsius, the concentration of ethanol in the aqueous ethanol solution is It is lower, less than 60% by weight.
　なお、ステップＳ１１においてエタノール水溶液が入れられる容器は、容器３６であっても、他の容器であってもよい。例えば、ステップＳ１１において容器３６にエタノール水溶液が入れられる場合、容器３６は、冷凍庫１の冷凍室３１内から取り外れされて、冷凍庫１の外で、容器３６にエタノール水溶液が入れられる。 The container in which the ethanol aqueous solution is placed in step S11 may be the container 36 or another container. For example, when the ethanol aqueous solution is put into the container 36 in step S11, the container 36 is removed from the freezing chamber 31 of the freezer 1, and the ethanol aqueous solution is put into the container 36 outside the freezer 1.
　ステップＳ１２において、種子を摂氏４００度以上５００度未満で熱分解し、粉砕して生成した粉体が、容器に入れられたエタノール水溶液に混合される。この場合、例えば、エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体であって、エタノール水溶液に対して０．１重量％乃至１．０重量％の粉体が混合される。 In step S12, the powder produced by thermally decomposing the seeds at 400 degrees Celsius or more and less than 500 degrees Celsius and pulverizing the seeds is mixed with the ethanol aqueous solution contained in the container. In this case, for example, it is a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius in an aqueous ethanol solution, and is 0.1% by weight to 1. 0% by weight of powder is mixed.
　ステップＳ１３において、水溶性のケイ素化合物が、容器に入れられたエタノール水溶液に混合される。この場合、例えば、エタノール水溶液に、エタノール水溶液に対して０．１重量％乃至１．０重量％の水溶性のケイ素化合物が混合される。 In step S13, the water-soluble silicon compound is mixed with the ethanol aqueous solution contained in the container. In this case, for example, 0.1% by weight to 1.0% by weight of a water-soluble silicon compound is mixed with the aqueous ethanol solution.
　ステップＳ１４において、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液を冷凍庫１の冷凍室３１内の容器３６に入れる。例えば、ステップＳ１１においてエタノール水溶液が冷凍庫１の外で容器３６に入れられた場合、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液が入れられた容器３６が冷凍庫１の冷凍室３１内に戻される。例えば、ステップＳ１１においてエタノール水溶液が容器３６とは別の容器に入れられた場合、容器３６とは別の容器に入れられた、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液が冷凍庫１の冷凍室３１内の容器３６に移される。 In step S14, an aqueous ethanol solution in which powder and a water-soluble silicon compound are mixed is placed in a container 36 in the freezer chamber 31 of the freezer 1. For example, when the aqueous ethanol solution is put into the container 36 outside the freezer 1 in step S11, the container 36 containing the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed is inside the freezer chamber 31 of the freezer 1. Returned to. For example, when the aqueous ethanol solution is placed in a container different from the container 36 in step S11, the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed, which is placed in a container different from the container 36, is stored in the freezer. It is transferred to the container 36 in the freezing chamber 31 of 1.
　ステップＳ１５において、冷凍庫１により、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液が摂氏零度より低い温度まで冷却される。例えば、エタノール水溶液のエタノールの濃度が６０重量％である場合、冷凍庫１により、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液が摂氏マイナス６０度まで冷却される。 In step S15, the freezer 1 cools the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed to a temperature lower than zero degrees Celsius. For example, when the concentration of ethanol in the aqueous ethanol solution is 60% by weight, the freezer 1 cools the aqueous ethanol solution in which the powder and the water-soluble silicon compound are mixed to -60 degrees Celsius.
　ステップＳ１６において、冷凍しようとする物品を密封容器に入れる。例えば、冷凍しようとする物品が、食品、化粧品または医療用の物品である場合、プラスチックフィルム若しくは金属箔またはこれらを多層に合わせたものを袋状その他の形に成形した容器であって、熱溶融により密封される容器である密封容器（いわゆるパウチ容器）に冷凍しようとする物品が入れられる。なお、密封容器は、樹脂、金属若しくはガラスまたはこれらの組合せからなる容器で、冷凍する物品がエタノール水溶液に直接触れないように密閉でき、冷凍庫１の冷凍室３１の温度までの冷却に耐えられるものであればよい。また、冷凍しようとする物品は、固体状であっても、液体状であってもよく、また、ゾル状またはゲル状であってもよい。 In step S16, put the article to be frozen in a sealed container. For example, when the article to be frozen is a food, cosmetic or medical article, it is a container formed of a plastic film or a metal foil or a multi-layered product thereof into a bag shape or other shape, and is heat-melted. The article to be frozen is put in a sealed container (so-called pouch container) which is a container sealed by. The sealed container is a container made of resin, metal, glass, or a combination thereof, which can be sealed so that the article to be frozen does not come into direct contact with the aqueous ethanol solution, and can withstand cooling to the temperature of the freezer chamber 31 of the freezer 1. It should be. Further, the article to be frozen may be in the form of a solid, a liquid, a sol or a gel.
　ステップＳ１７において、冷却されたエタノール水溶液に、密封容器に入れられた物品を浸けて、物品を冷凍し、冷凍品の製造の手順は終了する。 In step S17, the article placed in the sealed container is immersed in the cooled aqueous ethanol solution to freeze the article, and the procedure for manufacturing the frozen product is completed.
　このように、冷凍品を製造することができる。エタノール水溶液に浸けることで、より短時間により多くの熱が奪われるので、より速く冷凍品を製造することができる。粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液は、エタノール水溶液単独の場合に比較して、より低い温度まで凝固しないので、さらにより速く冷凍品を製造することができる。また、粉体と水溶性のケイ素化合物とが混合されたエタノール水溶液は、エタノール水溶液単独の場合に比較して、より低い温度まで凝固しないので、冷凍品の劣化をより少なくすることができ、より長い期間保存することができるようになる。 In this way, frozen products can be manufactured. By immersing in an aqueous ethanol solution, more heat is taken away in a shorter time, so that a frozen product can be produced faster. Since the ethanol aqueous solution in which the powder and the water-soluble silicon compound are mixed does not solidify to a lower temperature as compared with the case of the ethanol aqueous solution alone, a frozen product can be produced even faster. Further, since the ethanol aqueous solution in which the powder and the water-soluble silicon compound are mixed does not solidify to a lower temperature than the case of the ethanol aqueous solution alone, the deterioration of the frozen product can be further reduced, and more. It will be possible to store it for a long period of time.
　エタノールの濃度が６０重量％に近い、非危険物の６０重量％未満のエタノール水溶液を用いた場合、非危険物であり、摂氏マイナス６０度で凝集しないので、より安全に、寄生虫を死滅させ、菌の活動を抑制することができる。 When an aqueous ethanol solution with an ethanol concentration close to 60% by weight and less than 60% by weight of a non-dangerous substance is used, it is a non-dangerous substance and does not aggregate at -60 degrees Celsius, so that parasites are killed more safely. , The activity of the fungus can be suppressed.
　以上のように、冷凍庫１内の容器３６に溜められて冷却され、物品を浸けることにより物品を冷凍するための液状で用いられる冷却媒体３７は、エタノール水溶液と、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と、水溶性のケイ素化合物とを含む。 As described above, the cooling medium 37, which is stored in the container 36 in the freezer 1 and cooled and used as a liquid for freezing the article by immersing the article, contains an aqueous ethanol solution and plant seeds at 400 ° C. or higher. It contains a powder obtained by crushing a product thermally decomposed at less than 500 degrees and a water-soluble silicon compound.
　エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と水溶性のケイ素化合物とを混ぜることで、親水性の粉体がエタノール水溶液により長い時間分散し、また、水溶性のケイ素化合物が粉体の分散を促進させるので、粉体がエタノール水溶液の凝固を阻害して、エタノール水溶液単独の場合に比較して、より低い温度まで凝固しなくなり、より低い温度で使用することができるようになる。これにより、より速く物品を冷凍できる。 By mixing a powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 ° C. or higher and lower than 500 ° C. with a water-soluble silicon compound in an aqueous ethanol solution, the hydrophilic powder becomes longer than the aqueous ethanol solution. Since the time-dispersed and the water-soluble silicon compound promotes the dispersion of the powder, the powder inhibits the coagulation of the aqueous ethanol solution and does not coagulate to a lower temperature than the case of the aqueous ethanol solution alone. , Will be able to be used at lower temperatures. This allows the article to be frozen faster.
　また、使用する温度が同じであれば、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と水溶性のケイ素化合物とを混ぜることで、エタノール水溶液におけるエタノールの割合をより少なくすることができ、より安全に使用することができる。植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体および水溶性のケイ素化合物は、いずれも人体に無害なので、仮に、浸けられている物品に付着したとしても、より安全に取り扱うことができる。このように、より低い温度で凝固を抑制して、より安全に、より速く物品を冷凍できる。 Further, if the temperature used is the same, a powder obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius and crushing the product and a water-soluble silicon compound are mixed in an aqueous ethanol solution. The proportion of ethanol can be reduced and it can be used more safely. Since the powder and water-soluble silicon compound obtained by crushing the product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius are both harmless to the human body, it is assumed that they adhere to the immersed article. Can be handled more safely. In this way, it is possible to suppress coagulation at a lower temperature and freeze the article more safely and faster.
　粉体は、エタノール水溶液に対して０．１重量％乃至１．０重量％とし、水溶性のケイ素化合物は、エタノール水溶液に対して０．１重量％乃至１．０重量％とすることができる。このようにすることで、親水性の粉体がエタノール水溶液により長い時間分散し、また、水溶性のケイ素化合物が粉体の分散を促進させることができる。 The powder may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution, and the water-soluble silicon compound may be 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution. .. By doing so, the hydrophilic powder can be dispersed in the aqueous ethanol solution for a long time, and the water-soluble silicon compound can promote the dispersion of the powder.
　粉体は、エタノール水溶液に分散された場合、静置状態において２４時間以上懸濁の状態を維持するものとすることができる。このようにすることで、静置した場合でも、より長時間、粉体がエタノール水溶液の凝固を阻害できる。 When the powder is dispersed in an aqueous ethanol solution, the powder can be kept in a suspended state for 24 hours or more in a stationary state. By doing so, the powder can inhibit the coagulation of the aqueous ethanol solution for a longer period of time even when it is allowed to stand.
　粉体は、粒子径の分布の中心を示す代表値が１０μｍ以下であるものとすることができる。このようにすることで、粉体が分散しやすくなり、エタノール水溶液の凝固を阻害できる。 The powder can have a representative value of 10 μm or less, which indicates the center of the particle size distribution. By doing so, the powder can be easily dispersed and the coagulation of the aqueous ethanol solution can be inhibited.
　粉体は、１５重量％乃至１９重量％のカリウムと１重量％乃至３重量％のリンとを含むものとすることができる。このようにすることで、粉体が親水性となり、エタノール水溶液により長い時間分散し、エタノール水溶液の凝固を阻害できる。 The powder can contain 15% by weight to 19% by weight of potassium and 1% by weight to 3% by weight of phosphorus. By doing so, the powder becomes hydrophilic and can be dispersed in the ethanol aqueous solution for a long time to inhibit the coagulation of the ethanol aqueous solution.
　粉体は、ｐＨ７の溶液中においてマイナス０．５ｍＶのゼータ電位を生じさせるものとすることができる。このようにすることで、粉体が互いに反発しあい、分散しやすくなり、エタノール水溶液の凝固を阻害できる。 The powder can generate a zeta potential of minus 0.5 mV in a pH 7 solution. By doing so, the powders repel each other and are easily dispersed, and the coagulation of the aqueous ethanol solution can be inhibited.
　粉体は、豆類である種子を熱分解した生成物を粉砕してなるものとすることができる。このようにすることで、より確実に所望の特性の粉体を得ることができ、より低い温度で凝固を抑制して、より安全に、より速く物品を冷凍できる。 The powder can be made by crushing a product obtained by thermally decomposing seeds, which are beans. By doing so, it is possible to more reliably obtain a powder having desired properties, suppress coagulation at a lower temperature, and freeze the article more safely and faster.
　エタノール水溶液は、６０重量％未満のエタノールを含むものとすることができる。このようにすることで、エタノール水溶が、消防法において、非危険物として扱われ、より多くの冷却媒体３７をより簡単に扱うことができる。 The ethanol aqueous solution can contain less than 60% by weight of ethanol. By doing so, the water-soluble ethanol is treated as a non-dangerous substance in the Fire Service Act, and more cooling media 37 can be handled more easily.
　冷凍庫１は、内部の容器３６に冷却媒体３７を溜めることができる。より低い温度で冷却媒体３７の凝固を抑制して、より安全に、より速く物品を冷凍できる。 The freezer 1 can store the cooling medium 37 in the internal container 36. By suppressing the solidification of the cooling medium 37 at a lower temperature, the article can be frozen more safely and faster.
　エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体を混合し、エタノール水溶液に水溶性のケイ素化合物を混合し、粉体とケイ素化合物とが混合されたエタノール水溶液を液状のまま摂氏０度より低い温度に冷却し、物品を密封容器に入れ、密封容器に入れられた物品を冷却されたエタノール水溶液に浸けて冷凍させることで、冷凍品を製造することができる。 A powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 ° C. or higher and lower than 500 ° C. is mixed with an aqueous ethanol solution, and a water-soluble silicon compound is mixed with the aqueous ethanol solution. Frozen product by cooling the aqueous ethanol solution mixed with the above to a temperature lower than 0 degrees Celsius in a liquid state, placing the article in a sealed container, and immersing the article in the sealed container in the cooled aqueous solution of ethanol to freeze it. Can be manufactured.
　エタノール水溶液に対して０．１重量％乃至１．０重量％の粉体を混合し、エタノール水溶液に対して０．１重量％乃至１．０重量％の水溶性のケイ素化合物を混合することができる。 It is possible to mix 0.1% by weight to 1.0% by weight of powder with an aqueous ethanol solution and 0.1% by weight to 1.0% by weight of a water-soluble silicon compound with an aqueous ethanol solution. can.
　また、本発明の実施の形態は、上述した実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において種々の変更が可能である。 Further, the embodiment of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the present invention.
　１　冷凍庫，　１１　本体，　１２　扉，　１３　温度調節器，　３１　冷凍室，　３２　冷却器，　３３　コンデンシングユニット，　３４および３５　断熱材，　３６　容器，　３７　冷却媒体

  1 Freezer, 11 body, 12 doors, 13 temperature controller, 31 freezer, 32 cooler, 33 condensin unit, 34 and 35 insulation, 36 container, 37 cooling medium

Claims (11)

  1. 　冷凍庫内の容器に溜められて冷却され、物品を浸けることにより前記物品を冷凍するための液状で用いられる冷却媒体において、
    　エタノール水溶液と、
    　植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体と、
    　水溶性のケイ素化合物と
    　を含む冷却媒体。     In a cooling medium used as a liquid for freezing the article by storing it in a container in a freezer and cooling it, and immersing the article in it.
    With an aqueous ethanol solution
    A powder made by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius.
    A cooling medium containing a water-soluble silicon compound.
  2. 　請求項１に記載の冷却媒体において、
    　前記粉体は、前記エタノール水溶液に対して０．１重量％乃至１．０重量％であり、
    　前記水溶性のケイ素化合物は、前記エタノール水溶液に対して０．１重量％乃至１．０重量％である
    　冷却媒体。     In the cooling medium according to claim 1,
    The powder is 0.1% by weight to 1.0% by weight with respect to the aqueous ethanol solution.
    The water-soluble silicon compound is a cooling medium having an amount of 0.1% by weight to 1.0% by weight based on the aqueous ethanol solution.
  3. 　請求項１に記載の冷却媒体において、
    　前記粉体は、前記エタノール水溶液に分散された場合、静置状態において２４時間以上懸濁の状態を維持する
    　冷却媒体。     In the cooling medium according to claim 1,
    When the powder is dispersed in the aqueous ethanol solution, it is a cooling medium that maintains a suspension state for 24 hours or more in a stationary state.
  4. 　請求項１に記載の冷却媒体において、
    　前記粉体は、粒子径の分布の中心を示す代表値が１０μｍ以下である
    　冷却媒体。     In the cooling medium according to claim 1,
    The powder is a cooling medium having a representative value of 10 μm or less, which indicates the center of the particle size distribution.
  5. 　請求項１に記載の冷却媒体において、
    　前記粉体は、１５重量％乃至１９重量％のカリウムと１重量％乃至３重量％のリンとを含む
    　冷却媒体。     In the cooling medium according to claim 1,
    The powder is a cooling medium containing 15% by weight to 19% by weight of potassium and 1% by weight to 3% by weight of phosphorus.
  6. 　請求項１に記載の冷却媒体において、
    　前記粉体は、ｐＨ７の溶液中においてマイナス０．５ｍＶのゼータ電位を生じさせる
    　冷却媒体。     In the cooling medium according to claim 1,
    The powder is a cooling medium that produces a zeta potential of minus 0.5 mV in a pH 7 solution.
  7. 　請求項１に記載の冷却媒体において、
    　前記粉体は、豆類である前記種子を熱分解した前記生成物を粉砕してなる
    　冷却媒体。     In the cooling medium according to claim 1,
    The powder is a cooling medium obtained by crushing the product obtained by thermally decomposing the seeds of beans.
  8. 　請求項１に記載の冷却媒体において、
    　前記エタノール水溶液は、６０重量％未満のエタノールを含む
    　冷却媒体。     In the cooling medium according to claim 1,
    The ethanol aqueous solution is a cooling medium containing less than 60% by weight of ethanol.
  9. 　請求項１の冷却媒体が内部の容器に溜められている冷凍庫。 A freezer in which the cooling medium of claim 1 is stored in an internal container.
  10. 　エタノール水溶液に、植物の種子を摂氏４００度以上５００度未満で熱分解した生成物を粉砕してなる粉体を混合し、
    　前記エタノール水溶液に水溶性のケイ素化合物を混合し、
    　前記粉体と前記ケイ素化合物とが混合された前記エタノール水溶液を液状のまま摂氏０度より低い温度に冷却し、
    　物品を密封容器に入れ、
    　前記密封容器に入れられた物品を冷却された前記エタノール水溶液に浸けて冷凍させる
    　冷凍品の製造方法。     A powder obtained by crushing a product obtained by thermally decomposing plant seeds at 400 degrees Celsius or more and less than 500 degrees Celsius is mixed with an aqueous ethanol solution.
    A water-soluble silicon compound is mixed with the aqueous ethanol solution, and the mixture is mixed with a water-soluble silicon compound.
    The ethanol aqueous solution in which the powder and the silicon compound are mixed is cooled to a temperature lower than 0 degrees Celsius while remaining in a liquid state.
    Put the goods in a sealed container,
    A method for producing a frozen product, in which an article placed in a sealed container is immersed in a cooled aqueous solution of ethanol to freeze it.
  11. 　請求項１０に記載の冷凍品の製造方法において、
    　前記エタノール水溶液に対して０．１重量％乃至１．０重量％の前記粉体を混合し、
    　前記エタノール水溶液に対して０．１重量％乃至１．０重量％の水溶性の前記ケイ素化合物を混合する
    　冷凍品の製造方法。

          In the method for producing a frozen product according to claim 10,
    0.1% by weight to 1.0% by weight of the powder is mixed with the aqueous ethanol solution, and the powder is mixed.
    A method for producing a frozen product, in which 0.1% by weight to 1.0% by weight of the water-soluble silicon compound is mixed with the aqueous ethanol solution.
PCT/JP2021/017526 2020-05-13 2021-05-07 Cooling medium, freezer, and method for producing frozen product WO2021230154A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227859A (en) * 1996-02-22 1997-09-02 Tokyo Fine Chem Kk Coolant composition
JPH1067983A (en) * 1996-07-23 1998-03-10 Huels Ag Low-temperature retainer and sedimentation inhibitor
JPH10183109A (en) * 1996-12-20 1998-07-14 Hitachi Plant Eng & Constr Co Ltd Brine composition
JP2005113250A (en) * 2003-10-10 2005-04-28 Toyota Motor Corp Cooling liquid composition
JP2016129492A (en) * 2015-01-11 2016-07-21 鈴木 哲生 Method for producing individual frozen food product
JP2017136581A (en) * 2016-02-02 2017-08-10 早稲田ビジネスコンサルティング株式会社 Plant thermodecomposition powder composition, carbon-containing aqueous liquid article and manufacturing method of plant thermodecomposition powder composition
JP2018537551A (en) * 2015-11-11 2018-12-20 ロウ ホールディング ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Silicate-containing coolant concentrate
JP6854556B1 (en) * 2021-01-08 2021-04-07 感動創出工場ジーンファクトリー株式会社 Freezer and frozen product manufacturing method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227859A (en) * 1996-02-22 1997-09-02 Tokyo Fine Chem Kk Coolant composition
JPH1067983A (en) * 1996-07-23 1998-03-10 Huels Ag Low-temperature retainer and sedimentation inhibitor
JPH10183109A (en) * 1996-12-20 1998-07-14 Hitachi Plant Eng & Constr Co Ltd Brine composition
JP2005113250A (en) * 2003-10-10 2005-04-28 Toyota Motor Corp Cooling liquid composition
JP2016129492A (en) * 2015-01-11 2016-07-21 鈴木 哲生 Method for producing individual frozen food product
JP2018537551A (en) * 2015-11-11 2018-12-20 ロウ ホールディング ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Silicate-containing coolant concentrate
JP2017136581A (en) * 2016-02-02 2017-08-10 早稲田ビジネスコンサルティング株式会社 Plant thermodecomposition powder composition, carbon-containing aqueous liquid article and manufacturing method of plant thermodecomposition powder composition
JP6854556B1 (en) * 2021-01-08 2021-04-07 感動創出工場ジーンファクトリー株式会社 Freezer and frozen product manufacturing method

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