JP5664994B2 - Ozone ice with high bubble content of ice, method and apparatus for producing the ozone ice - Google Patents

Description

  The present invention relates to ozone ice having a high bubble content of ice, and a method and apparatus for producing the ozone ice.

  At present, it has been confirmed that ozone water in which ozone gas having a sterilizing and deodorizing action is dissolved in water is effective in maintaining the freshness of fresh food, and its use is expanding. However, since ozone decomposes into oxygen over time, it is safe, but it is difficult to maintain its effect. Therefore, attention has been focused on ozone ice in which ozone is enclosed as bubbles in ice for the purpose of maintaining and cooling the ozone (see, for example, Patent Documents 1 and 2). If this ozone ice has a high bubble content and is manufactured easily and inexpensively, it is expected that the transport and storage efficiency (including cost) of food will be dramatically improved and will greatly contribute to the food distribution system. Is done.

JP2007-225127A JP-A-2005-77040

  In Patent Document 1, water containing microbubbles is injected into the inside of the container, or microbubbles are mixed into the water injected into the inside of the container, cooled from the surroundings, and the water is frozen in a state containing microbubbles. Thus, a method for producing gas-containing ice (ozone ice) is disclosed. However, in the document 1, a manufacturing apparatus having a structure in which a microbubble generator and a water supply device are connected to a cylindrical ice manufacturing container having an open top surface and provided with a heating unit and a cooling unit on a side surface is used. Microbubbles are cooled from the periphery of the cylindrical ice manufacturing container (see FIGS. 1 to 3), and the microbubbles are almost uniformly distributed in the water inside the cylindrical ice manufacturing container. It is possible to obtain ozone ice with a high bubble content of ice that is not unevenly distributed locally. Specifically, the gas content of ice produced from water in which conventional air is dissolved is 3%, whereas the gas content of ice produced from water containing microbubbles of air is 6% ( It is 2 times higher than the conventional technology. In addition, it is described that the ozone content in the ozone ice at this time is 30 mg / l at the maximum (1.4% in terms of volume).

  However, in Cited Document 1, while cooling from the periphery of a cylindrical ice manufacturing container whose upper surface is open, the water contained inside the cylindrical ice manufacturing container is dispersed in a substantially uniform manner to freeze water contained therein. In order to produce ozone-containing ice, the efficiency of capturing microbubbles in the ice is poor, and as a result, the bubble content of ice can only achieve a maximum of 6% by volume and higher. There is a problem that it is very difficult to produce ice having a bubble content in terms of the apparatus configuration or the manufacturing method.

  On the other hand, the ozone ice generation method includes a sealed pressurization method, which was commercialized in 2005, and the manufacturing method described in the cited document 2 also uses this method. This method has a cylindrical container provided with a hermetic lid that can be opened and closed on one side. On one side or the other side of the cylindrical container, ozone supplied by a pump pressurizes ozone into water and dissolves ( The upper part of a cylindrical container that has an ozone water injection port (dissolved) and is arranged in an upright state is capable of releasing internal gas and injecting ozone or oxygen from the outside. A mouth is provided (FIG. 1), and ozone water injected into a cylindrical container is cooled and frozen in a pressurized state to generate ozone ice in which bubbles containing ozone generated in the process are refined.

  However, in this method, the higher the pressure and the higher the cooling rate, the higher the ozone concentration in ice. For this reason, an apparatus for generating high-concentration ozone ice has a high pressure resistance, cooling at a low temperature, miniaturization of ice size (increase in the number of ice-making tubes; here, for ice-making tubes, see FIG. 1 of JP-A-2008-64356). Etc.), for example, the size is increased and the ice making efficiency is reduced (only ozone ice with a low bubble content can be obtained). For the above reasons, it is difficult to reduce the initial and operating costs of the sealed pressurized ozone ice generator.

  Furthermore, in Cited Document 2, since only ozone water that is dissolved (dissolved) by pressurizing ozone into water is used without using ozone-containing microbubble mixed water, the bubble content of ice is increased. There was a problem that could not be. Specifically, from FIG. 3 and paragraph “0050”, the maximum ozone concentration in ozone ice is 5.37 mg / l, which is only 0.2 to 0.3% by volume in terms of volume as in the case of the cited reference 1. Absent. There is a problem that ozone can be contained only at a concentration of about 1/5 of ozone ice using the ozone-containing microbubbles of Cited Document 1.

  Accordingly, an object of the present invention is to provide ozone ice having a high bubble content rate of ice, and a method and apparatus for producing the ozone ice.

  Moreover, in the ozone ice manufacturing apparatus and manufacturing method of the present invention, ozone microbubble diameters of about 10 μm to 100 μm (usually about 20 μm is the center of the particle size distribution) are mixed in water to trap the bubbles on the ice making surface. An object of the present invention is to develop a manufacturing apparatus and a manufacturing method capable of generating ozone ice having a high bubble content of ice.

  It is another object of the present invention to provide an apparatus for producing ozone ice that is capable of making ice under normal pressure without using a pressurized container and that can optimally control the ice making speed.

  Another object of the method for producing ozone ice of the present invention is to provide a method capable of optimally controlling the concentration of ozone by controlling the amount of microbubbles in the liquid.

  Therefore, the object of the present invention is achieved by (1) ozone ice characterized in that the gas content (volume ratio) of ice is higher than 6% by volume.

  The object of the present invention is also achieved by (2) ozone ice as described in (1) above, wherein the gas content (volume ratio) of the ice is in the range of 7 to 42% by volume. is there.

  The object of the present invention is also (3) The ozone ice according to (1) or (2) above, wherein the average value of the bubble size (bubble diameter) of the ice is in the range of 70 to 135 μm. Is achieved.

  The object of the present invention is (4) the ozone ice according to any one of the above (1) to (3), wherein the ice is water obtained by removing chlorine from tap water or groundwater. Can also be achieved.

  The object of the present invention is achieved by (5) an ozone ice slurry characterized in that the gas content (volume ratio) in the ice slurry is higher than 6% by volume.

  The object of the present invention is also achieved by (6) the ozone ice slurry according to (5) above, wherein the gas content (volume ratio) in the ice slurry is in the range of 7 to 42% by volume. Is.

  The object of the present invention is to provide (7) ozone ice as described in (5) or (6) above, wherein the additive capable of forming an ozone ice slurry is contained in an amount exceeding 0% by volume up to 25% by volume. It can also be achieved with a slurry.

  Another object of the present invention is (8) the ozone ice as described in (5) or (6) above, which is produced from the ozone ice of (1) to (4) above using a harvest method. It can also be achieved with a slurry.

Another object of the present invention is (9) an ozone raw material part,
An ozone generator for generating ozone from the raw material supplied from the ozone raw material section;
A microbubble mixing device that generates microbubble mixed water from ozone-containing gas generated by the ozone generator, ozone water supplied from a water tank and / or water supplied from outside,
(A) The tip of the pipe for supplying the microbubble-mixed water generated by the microbubble-mixing device is in the tank so that microbubbles floating from the microbubble-mixed water can be captured under the cooling surface of the cooling member. And (b) a water tank in which the cooling member is disposed in an upper part or a central part of the tank,
A refrigerant circulation device that circulates a refrigerant in a circulation flow path inside the cooling member to cool at least the cooling surface of the cooling member;
It is achieved by an apparatus for producing ozone ice characterized by having

  Another object of the present invention is (10) the cooling surface angle of the cooling member is a flat plate-shaped cooling member installed in the range of 0 ° to 60 °, as described in (9) above It can also be achieved by an ozone ice production device.

  Another object of the present invention is (11) the cooling surface angle of the cooling member is a flat plate-shaped cooling member installed in a range of 10 ° to 15 °, as described in (10) above It can also be achieved by an ozone ice production device.

  Another object of the present invention is (12) the ozone according to any one of (9) to (11) above, further comprising a power supply device for applying a voltage to the cooling member. It can also be achieved by an ice production device.

  Another object of the present invention is (13) The apparatus for producing ozone ice according to (12) above, wherein the DC voltage applied to the cooling surface of the cooling member using the power supply device is 100 to 300V. Can also be achieved.

  Another object of the present invention is (14) On the path for supplying tap water from the outside to the microbubble mixing device, if necessary, ozone water is supplied (circulated) from the water tank to the microbubble mixing device. It is also achieved by the ozone ice manufacturing apparatus according to any one of (9) to (13) above, wherein a chlorine removing means is installed on the route.

  Another object of the present invention is (15) that the microbubble diameter in the microbubble mixed water produced by the microbubble mixing apparatus is 10 to 100 μm, and the average value of the microbubble diameter is 20 μm. It is also achieved by the ozone ice manufacturing apparatus according to any one of the above (9) to (14).

  Another object of the present invention is (16) an exhaust pipe for exhausting the component gasified by floating microbubbles in the water mixed with microbubbles supplied into the water tank from the water tank to the outside of the system. And / or a supply pipe for supplying a component gasified by floating microbubbles in the water mixed with microbubbles from the inside of a water tank to the ozone generator. It is achieved by the ozone ice manufacturing apparatus according to any one of 9) to (15).

  Another object of the present invention is as follows: (17) The ozone generator is further provided with a moisture removing means in a path for supplying a gasified component in which microbubbles in the water mixed with microbubbles float on the liquid surface of the water tank. The present invention is also achieved by the ozone ice manufacturing apparatus according to any one of (9) to (16) above.

  Another object of the present invention is as follows: (18) As the moisture removing means, a location having an enlarged diameter is provided in the gasified component supply path, and the gasified component is cooled and dehumidified at the enlarged location. (17), characterized in that a humectant for adsorbing and removing moisture from the gasified component is installed in a Peltier element for this purpose and / or a supply path for the gasified component. It can also be achieved by the described ozone ice production apparatus.

  Another object of the present invention is (19) the manufacturing apparatus according to the above (9) to (18), a storage part of an additive that can be further made into an ozone ice slurry, and a microbubble mixing apparatus from the storage part. And a supply path provided with a flow rate adjusting device for supplying the additive at a predetermined ratio (volume ratio) to water supplied to the mixing device. It is also achieved by the device.

  Another object of the present invention is to (20) the manufacturing apparatus according to the above (9) to (18), further to (a) a harvest method with respect to ozone ice generated on the cooling surface of the cooling member. An ozone ice slurry comprising an ice scraping device for scraping off the ozone ice that has been peeled off into a slurry, or (b) an ice scraping device for directly scraping into slurry by a scraping method. This can also be achieved by the manufacturing apparatus.

Still another object of the present invention is to provide (21) an ozone generation stage in which ozone is generated by an ozone generator from a raw material supplied from an ozone raw material section;
Bubbles for introducing microbubble mixed water by introducing ozone-containing gas generated in the ozone generation stage, water circulated (supplied) from a water tank and / or water supplied from the outside into a microbubble mixing device Mixed water generation stage;
(A) The tip of the pipe for supplying the microbubble-mixed water generated by the microbubble-mixing device is in the tank so that microbubbles floating from the microbubble-mixed water can be captured under the cooling surface of the cooling member. And (b) a bubble-mixed water supply for supplying microbubble-mixed water generated in the bubble-mixed water generation stage to a water tank in which the cooling member is disposed in the upper or central portion of the tank. Stages,
By returning (supplying) the ozone water in the water tank to the microbubble mixing device and supplying (circulating) the bubble mixed water generated and regenerated in the water tank again, microbubbles are formed on the cooling surface side of the cooling member. While maintaining the accumulated (captured) state, the refrigerant is circulated from the refrigerant circulation device to the circulation flow path inside the cooling member to cool at least the cooling surface of the cooling member, and air bubbles are contained on the cooling surface side. An ozone ice production stage to produce the depleted ozone ice;
It is achieved by a method for producing ozone ice characterized by having

  Still another object of the present invention is (22) the cooling member is a flat cooling member, and the cooling surface angle of the cooling member is set in a range of 0 ° to 60 °. This can also be achieved by the method for producing ozone ice as described in (21) above.

  According to still another object of the present invention, (23) the cooling surface angle of the cooling member is set in the range of 10 ° to 15 °. This can also be achieved by the manufacturing method.

  Still another object of the present invention is (24) the above (21) to (23), further comprising a voltage applying step of applying a voltage to the cooling member using a power supply device during the ozone ice generation stage. ) Is also achieved by the method for producing ozone ice according to any one of items 1).

  Still another object of the present invention is as described in (24) above, wherein in the voltage application step, a DC voltage applied to the cooling surface of the cooling member using a power supply device is 100 to 300V. This can also be achieved by the production method of ozone ice.

  According to still another object of the present invention, (26) in the bubble mixed water generation stage, the micro bubble mixing device is further provided on a path for supplying tap water from the outside to the micro bubble mixing device. Any one of the above (21) to (25), further comprising a step of removing chlorine using a chlorine removing device installed on a path through which ozone water is supplied (circulated) from the water tank. It can also be achieved by the method for producing ozone ice described in item 1.

  Still another object of the present invention is (27) the microbubble diameter in the microbubble mixed water generated by the microbubble mixing apparatus in the bubble mixed water generation stage is 10 to 100 μm, and the microbubble diameter The average value is 20 μm, and it is also achieved by the method for producing ozone ice according to any one of the above (21) to (26).

  Still another object of the present invention is to provide (28) a component (ozone + oxygen) obtained by gasification of microbubbles in bubble-mixed water supplied into a water tank that floats on the liquid surface during the ozone ice generation stage. Exhaust process for exhausting out of the system from the water tank and / or gasified component for supplying the ozone generation apparatus from the water tank to the gasified component that the microbubbles in the microbubble mixed water float on the liquid surface It is achieved by the method for producing ozone ice according to any one of the above (21) to (27), further comprising a recycling step.

  Another object of the present invention is (29) In the path for supplying the gasified component by the microbubbles in the water mixed with microbubbles floating on the liquid level of the water tank during the ozone ice generation stage. The method for producing ozone ice according to any one of (21) to (28) above, further comprising a step of removing moisture from the gasified component using a moisture removing device installed in Can also be achieved.

  Still another object of the present invention is as follows: (30) As the moisture removing means, (a) a portion having a diameter expanded in a supply path of a component gasified by the microbubbles is provided, and the gasification is performed at the expanded portion. A Peltier element for cooling and dehumidifying the component, and / or (b) a moisture absorbent for adsorbing and removing moisture from the gasified component in the supply path of the component gasified by the microbubbles. This can also be achieved by the method for producing ozone ice as described in (29) above.

  Furthermore, still another object of the present invention is (31) In the manufacturing method according to (21) to (30) above, an additive storage unit that can be further made into an ozone ice slurry during the bubble mixed water generation step. And supplying the additive at a predetermined ratio (volume ratio) to the flow rate of water supplied to the mixing device through a supply path provided with a flow rate adjusting device in the microbubble mixing device. This can also be achieved by a method for producing an ozone ice slurry.

  Still another object of the present invention is to (32) in the manufacturing method according to the above (21) to (30), with respect to ozone ice generated on the cooling surface of the cooling member; The ozone ice peeled by the method is scraped and slurried using an ice scraper, or (b) the slurry is scraped and slurried directly using an ice scraper by the scraping method. This can also be achieved by the production method of ozone ice slurry.

  Still another object of the present invention is to provide (33) the manufacturing apparatus according to any one of (9) to (20) above, and any one of (21) to (32) above. A bubble-containing ice or ice slurry obtained by ice making or ice making slurry using the production method described above, wherein the bubble content (volume ratio) of the ice or ice slurry is higher than 6% by volume. And ice or ice slurry.

  Still another object of the present invention is to provide (34) the manufacturing apparatus according to any one of (9) to (20) above, and any one of (21) to (32) above. Using the described manufacturing method, flavor and fruit juice concentrates are produced by injecting flavored gas into a flavored gas or ice-making slurry by injecting a flavored gas into ice-making or ice-making slurry. A certain ice confectionery can also be achieved by a taste and fragrant ice confectionery characterized in that the bubble content (volume ratio) of the ice or ice slurry is higher than 6% by volume.

  Still another object of the present invention is to provide (35) the manufacturing apparatus according to any one of (9) to (20) above, and any one of (21) to (32) above. Using the described production method, colored gas is formed from ice or ice slurry containing colored bubbles, which is made by injecting colored gas into a colored liquid by water or food additives to make ice or ice making slurry. It is also achieved by a colored ice confectionery characterized in that the bubble content (volume ratio) of the ice or ice slurry is higher than 6% by volume.

  According to the ozone ice of the present invention, it is possible to realize an ice gas content (volume ratio) that is twice as high as that of Patent Document 1. In addition, it is also possible to effectively develop a desired sterilization / deodorization effect by mixing normal inexpensive ice and ozone ice having a high ice gas content of the present invention at an appropriate ratio. Depending on the type of fresh food and the storage / transportation method, etc.) As a result, transportation and storage efficiency (including cost) as a whole can be dramatically improved, which can greatly contribute to the food distribution system.

  According to the ozone ice manufacturing apparatus and the manufacturing method using the apparatus of the present invention, ozone microbubbles having an average of about 20 μm are mixed in water, and the ozone microbubbles are captured on the cooling surface (ice-making surface) of the cooling member. The purpose is to develop an apparatus and method for producing ozone ice having a high gas content of ice. When mixed in water in the form of a microbubb, the specific surface area is large, so the contact area with water increases, and it becomes easy to dissolve in water. In the production apparatus and production method of the present invention, ice making can be performed under normal pressure, and the ice making speed can be reduced. Therefore, it becomes a system with high ice making efficiency, and a small system can be constructed. In addition, the concentration of ozone can be controlled by controlling the amount of microbubbles in the liquid. Moreover, since the manufacturing apparatus of the present invention can be very miniaturized, it can be sufficiently installed along with the existing western apparatus. As a result, as described above, normal inexpensive ice and ozone ice having a high ice gas content of the present invention are mixed at an appropriate ratio, and both ices are moved (transferred). A system (manufacturing equipment) that is more productive than the entire production system (manufacturing equipment, manufacturing method), including the use of existing systems (manufacturing equipment, manufacturing method) that normally do not need to produce ice. , Manufacturing method).

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view schematically showing a typical embodiment of an ozone ice production apparatus according to the present invention, which is an apparatus provided with a flat plate-like cooling member as a cooling member. FIG. 2A is a schematic view schematically showing a typical embodiment of a cooling member used in the present invention, and FIG. 2A1 is a schematic view of a flat plate-like cooling member. FIG. 2A2 is a schematic diagram showing a state in which a flat cooling member is provided in a water tank horizontally (cooling surface angle of the cooling member 0 °; downward cooling). FIG. 2A3 is a schematic diagram illustrating a state in which the water tank is provided with a cooling surface angle of 10 ° (downward cooling) of the flat cooling member. FIG. 2A4 shows a conventional example in which microbubbles are mixed into water injected into a cylindrical container (water tank) and cooled from the periphery of the container (water tank) in the same manner as the existing manufacturing apparatus of Patent Document 1 and the like. Schematic showing a state in which the cooling surface angle of the flat cooling member inside the water tank is arranged near the periphery (side surface) in the water tank so that the cooling surface angle is 90 ° (lateral cooling = cooling from around the container) It is. FIG. 2B1 is a schematic view of a hemispherical cooling member. FIG. 2B2 is a schematic diagram showing a state in which the hemispherical cooling member of FIG. 2B1 is provided in the water tank so that the spherical cut surface is a horizontal bottom surface (ice is generated inside). FIG. 2C1 is a schematic view of an upper sphere shaped cooling member cut horizontally from the surface of the sphere at a depth of 1/3 of the diameter. FIG. 2C2 is a schematic diagram showing a state in which the upper spherical cooling member of FIG. 2C1 is provided in the water tank so that the sphere cut surface becomes a horizontal bottom surface (ice is generated inside). FIG. 2D1 is a schematic view of a cylindrical cooling member. FIG. 2D2 is a schematic diagram illustrating a state in which the cylindrical cooling member of FIG. 2D1 is provided in the water tank so as to face sideways (the cylindrical center axis is parallel: ice is generated inside). FIG. 2E1 is a schematic view of a cooling member having a triangular roof shape (a shape obtained by folding a flat plate in half so that the side surface is triangular). FIG. 2E2 is a schematic view showing a state in which a cooling tank having a shape in which the flat plate of FIG. 2E1 is folded in half so that the side surface is triangular is provided in the water tank so that the top of the triangular roof is at the top. FIG. 2F1 is a schematic view of a curved flat plate-shaped cooling member 27d. FIG. 2F2 is a schematic diagram showing a state in which the curved flat plate-shaped cooling member 27d of FIG. 2F1 is provided in the water tank 33 in a curved flat-plate inverted U shape (downward cooling). FIG. 2G1 is a schematic view of a semi-cylindrical cooling member 27d. FIG. 2G2 shows a state in which the water tank 33 is provided so that the semicylindrical cooling member 27d of FIG. 2G1 faces sideways (the lateral end surface is an inverted U shape and the semicylindrical center axis is parallel; ice is generated inside). FIG. However, any cooling member 27 in FIGS. 2A1 to 2G1 does not show the refrigerant flow path inside. In Experimental Example 1, as a cooling member, a flat cooling member was horizontal (cooling surface angle was 0 ° = horizontal wall), and the cooling member was vertical (cooling surface angle was 90 ° = vertical wall). It is drawing (graph) showing the bubble content rate (volume%) in ice at the time. In Experimental Example 2, as a cooling member, a flat cooling member was made horizontal (cooling surface angle 0 ° = horizontal wall), and the cooling member was made vertical (cooling surface angle 90 ° = vertical wall). It is drawing (graph) showing the mode of change of the bubble content rate (volume%) in ice at the time of changing a cooling surface angle (degree) to a cooling member. FIG. 4A is a drawing showing a photograph of an ice plane (surface) generated from above when the cooling surface angle of the cooling member of FIG. 3 is 0 ° (horizontal wall). 4B is a drawing showing a photograph of the side cross section (transverse cross section) of the ice of FIG. 4A taken from the side. Here, the upper part of the drawing of FIG. 4B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 5A is a drawing showing a photograph of the ice plane (surface) generated from the upper side with the cooling surface angle of the cooling member of FIG. 3 being 10 °. 4B is a drawing showing a photograph taken from the side of the ice of FIG. 4A. Here, the upper part of FIG. 5A is the lower side when tilted by 10 °, and the lower part of the drawing is the upper side when tilted by 10 °. The upper part of the drawing in FIG. 5B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 6A is a drawing showing a photograph of a plane (surface) of ice generated from the cooling member of FIG. 3 with a cooling surface angle of 15 ° taken from above. 6B is a drawing showing a photograph taken from the side of the ice of FIG. 6A. Here, the upper part of FIG. 6A is the lower side when tilted by 15 °, and the lower part of the drawing is the upper side when tilted by 15 °. The upper part of the drawing in FIG. 6B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 7A is a drawing showing a photograph of the plane (surface) of ice generated from the cooling member of FIG. 3 with a cooling surface angle of 20 ° taken from above. FIG. 7B is a drawing showing a photograph taken from the side of the ice of FIG. 7A. Here, the upper part of FIG. 7A is the lower side when tilted by 20 °, and the lower part of the drawing is the upper side when tilted by 20 °. The upper part of the drawing of FIG. 7B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 8A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with a cooling surface angle of 25 ° of the cooling member of FIG. 3. FIG. 8B is a drawing showing a photograph taken from the side of the ice of FIG. 8A. Here, the upper part of the drawing in FIG. 8A is the lower side when tilted by 25 °, and the lower part of the drawing is the upper side when tilted by 25 °. The upper part of the drawing in FIG. 8B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 9A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with the cooling surface angle of the cooling member of FIG. 3 being 30 °. FIG. 9B shows a photograph taken from the side of the ice of FIG. 9A. Here, the upper part of FIG. 9A is the lower side when tilted by 30 °, and the lower part of the drawing is the upper side when tilted by 30 °. The upper part of the drawing of FIG. 9B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 10A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with a cooling surface angle of 45 ° of the cooling member of FIG. 3. FIG. 10B shows a photograph taken from the side of the ice in FIG. 10A. Here, the upper part of FIG. 10A is the lower side when tilted by 45 °, and the lower part of the drawing is the upper side when tilted by 45 °. The upper part of the drawing of FIG. 10B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 11A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with the cooling surface angle of the cooling member of FIG. 3 being 90 °. FIG. 11B is a drawing showing a photograph taken from the side of the ice of FIG. 11A. Here, the upper part of FIG. 11A is the lower side when tilted by 90 °, and the lower part of the drawing is the upper side when tilted by 90 °. The upper part of the drawing in FIG. 11B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side. FIG. 12A shows the applied voltage (V) to the cooling member and the wall surface (cooling surface or ice making surface) when the applied voltage (V) to the cooling member is changed in the range of 0 V (no application) to 400 V. It is drawing (graph) showing the relationship of the average bubble ratio (volume%) in). FIG. 12B shows the air bubble capture rate (%) when the cooling surface angle is 0 ° (horizontal wall) and 90 ° (vertical wall) when the applied voltage (V) to the cooling member is 0 V (no application). It is drawing (graph) showing the relationship of these. It is drawing (graph) showing the time-dependent change of a dimensionless ozone water density | concentration.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.
[I] Ozone ice (1) Gas content of ice (volume ratio)
The ozone ice of the present invention is characterized in that the gas content (volume ratio) of ice is higher than 6% by volume. The gas content (volume ratio) of ice is preferably 7 to 42% by volume, more preferably 20 to 33% by volume, especially 22 to 28% by volume. When the gas content (volume ratio) of ice is 6% by volume or less, the gas content (ozone concentration) in ozone ice is not sufficient, and the effective period of the desired sterilization / deodorization action by ozone ice is short, Even when a large amount of expensive ozone ice is used, there is still a problem that it cannot maintain sufficient sterilization and deodorization as well as sufficient cooling during transport and storage of fresh food. In addition, since the gas content (ozone concentration) in ozone ice is not sufficient, it is extremely difficult to mix it with normal inexpensive ice, and supply only a large amount of expensive ozone ice and replenish it frequently. Therefore, there is a problem that the cost required for cold preservation, sterilization and deodorization of fresh food during storage and transportation becomes very high. As a result, it can be said that overall transportation and storage efficiency (including cost) is reduced, and a sufficient contribution to the food distribution system cannot be achieved. On the other hand, the upper limit value of the gas content rate (volume ratio) of ice is not limited, and even if it is in a range exceeding 42% by volume, it has a higher utility value as long as the effects of the present invention are not impaired. Become. That is, it is extremely effective in that the ozone concentration increases as the gas content increases. On the other hand, with ozone ice with a high gas content, the proportion of ice in the unit volume tends to decrease relatively, and the cooling time tends to decrease. What is necessary is just to determine the gas content rate (volume ratio) of these suitably. In addition, by using the production method and production apparatus of the present invention, it is possible to sufficiently produce ozone ice having a higher value in which the gas content (volume ratio) of ice exceeds 42% by volume. For example, as shown in FIG. 12A, the bubble content is 28% by volume when the cooling surface angle is 0 ° and 22% by volume when the cooling surface angle is 10 °, as shown in FIG. Furthermore, it can be said that about 1.5 times or more (28 × 1.5 = 42% by volume or more, 22 × 1.5 = 33% by volume or more) of gas can be contained, and further, ice making time, cooling temperature during ice making, etc. By adjusting, a higher bubble content can be obtained. Furthermore, it is possible to further increase the ozone concentration in the gas by removing chlorine from the tap water and reusing the discharged ozone gas.

  Until now, the research on the bubbles taken into ice is only about the precipitation of fine particles and dissolved air (see Patent Document 2). The invention relates to bubbles in water, which is the subject of the present invention, which is only disclosed in Patent Document 1, and is 28% by volume which is nearly five times the 6% by volume of ice gas content, which was impossible in Cited Document 1. The ozone ice of the present invention is very original and meaningful (useful) in that a high gas content (= high ozone content concentration) is realized in a very short ice making time (40 minutes; see FIG. 2A in Example 1). It is.

(1a) Concentration of ozone water with bactericidal / deodorizing effect (a) The bactericidal effect of ozone water is 0.3 to 0.5 ppm for 30 to 60 seconds for E. coli, and 0 for lactic acid bacteria. .3 to 1.0 ppm for 30 to 60 seconds. The deodorizing effect of ozone water is 0.5 to 5 ppm.

  (B) The bactericidal / deodorizing effect of ozone gas is about 0.1 to 1 ppm.

(C) Ozone half-life In water, it is several minutes to a sufficient level, and in gas, it is several hours to several tens of hours. However, since it varies greatly depending on the conditions, it is desirable to conduct preliminary experiments for each application and confirm how long sufficient cooling and sterilizing / deodorizing effects have continued.

(D) Ozone concentration in ozone ice bubble and ozone ice dissolved ozone concentration at 0 ° C. The total of dissolved ozone concentration and bubble-containing ozone concentration in ozone ice is about 25 ppm at present. If the total of the dissolved ozone concentration of ozone ice and the bubble-containing ozone concentration is about 1 to 5 ppm, the bactericidal and deodorizing action can be sufficiently exerted by the bubble-containing ozone and the ozone water when dissolved. It can also be used as mixed ice with normal ice. On the other hand, if the dissolved ozone concentration of ozone ice is less than or equal to the saturated concentration, it can be dissolved at a saturated concentration without becoming supersaturated. It can be demonstrated. It can also be used as mixed ice with normal ice.

Although the ozone concentration in the bubbles is difficult to measure, it is considered to be the same concentration as the ozone gas obtained by the maximum ozone generator, and considering the high bubble content of the ozone ice generated by this measuring device, it is sufficient The ozone concentration in the air bubbles is obtained. Therefore, if the confidentiality of the food cold storage container is ensured even after the ozone ice is completely dissolved, the ozone half-life gas of (c) is several hours to several tens of hours. If it is used for cold preservation and sterilization / deodorization of fresh foods, it can be said that it is possible to maintain chilling and sterilization / deodorization for a long period of up to several tens of hours.
(2) Average value of ice bubble size (bubble diameter) The average value of the bubble size (bubble diameter) of the ice of the present invention is in the range of 70 μm to 135 μm, preferably 70 μm to 125 μm, more preferably 70 to 80 μm. desirable. If the average value of the bubble size (bubble diameter) of ice is within the above range, it is contained in the ozone ice in a state of being distributed almost evenly, and each independent bubble pops at an appropriate interval when the ice is melted ( It is possible to continue to release (supply) an appropriate amount of ozone-containing gas to the surrounding fresh foods, and to continue to effectively maintain long-term cooling, sterilization and deodorization during the preservation and transportation of fresh foods. It is excellent in that it can be done. However, as long as the operational effects of the present invention are not impaired, the present invention is not limited to the above range.

  In addition, the average value of the bubble size (bubble diameter) of ice can be controlled (adjusted) by making the injection method of ozone microbubble mixed water continuous or intermittent. In particular, by adjusting the intermittent time and the number of intermittent times, the average value of the ice bubble size (bubble diameter) can be controlled. However, as long as the effects of the present invention are not impaired, the present invention is not limited to the above range.

  In addition, the average value of the bubble size (bubble diameter) of ice can be calculated (measured) by cutting the ice, taking a photograph of the cross section, subjecting the photograph to image analysis processing, and subjecting the photograph to particle analysis processing.

(3) Ozone ice made of tap water from which chlorine has been removed The ozone ice of the present invention is preferably made using tap water or water from which chlorine has been removed from groundwater. Pure water such as distilled water and ion-exchanged water has a higher production cost than tap water and groundwater, and is very expensive. On the other hand, it is inexpensive to use inexpensive tap water or groundwater, and water that has been adsorbed, decomposed, or removed by means of hollow fiber (fiber bundle) filters used in water purifiers or ultraviolet irradiation. In addition, by using tap water or groundwater from which chlorine has been removed, ozone can be effectively prevented from being decomposed due to the reaction between ozone and chlorine in ozone water, resulting in a decrease in ozone concentration. It is also excellent in that the effect of increasing the amount of ozone-containing microbubbles is obtained (see Example 5 and FIG. 4).

(4) Combination of ozone ice having high ice gas content of the present invention and ordinary inexpensive ice (adjustment of mixed ice)
By using ozone ice having a high gas content of the ice of the present invention and ordinary inexpensive ice in an appropriate ratio, the desired sterilization / deodorizing action can be effectively expressed. Depending on the type and storage / transportation method). As a result, transportation and storage efficiency (including cost) as a whole can be dramatically improved, which can greatly contribute to the food distribution system. In particular, the above (1a) sterilization / deodorization ozone water concentration, (a) sterilization effect of ozone water, (b) sterilization / deodorization effect of ozone gas, and (c) ozone half-life, etc. What is necessary is just to adjust mixed ice that can keep the cold preservation and sterilization / deodorizing effect for a long period of time according to the use and that is cheaper. Thereby, it is excellent at the point which can adjust the mixed ice which satisfies both cold preservation, sterilization and deodorizing effect, and cost reduction.

(5) Use Application The use application of the ozone ice having the high ice gas content of the present invention or the above mixed ice is mainly for the cold preservation effect and the sterilization / deodorization action for maintaining the freshness of fresh food. The fresh food that can use the ozone ice having the high gas content of the ice and the above mixed ice of the present invention is not particularly limited. For example, fresh fish shellfish, fresh vegetables and fruits (in this case, vegetables and fruits ( (For example, leaf vegetables etc.) should be wrapped and used with a gas (especially ozone gas) permeable film etc. for the purpose of preventing them from getting wet and becoming painful.In this case, only ozone gas contained in ozone ice bubbles , Raw meat (again, raw meat such as beef is wrapped with a gas (especially ozone gas) permeable film (wrap film) in order to prevent it from getting wet and becoming painful) In this case, too, only ozone gas contained in the bubbles of ozone ice will act effectively.)
[Ia] Ozone ice slurry (1) Gas content (volume ratio) of ozone ice slurry
The ozone ice slurry of the present invention is characterized in that the gas content (volume ratio) in the ice slurry is higher than 6% by volume. In the present embodiment, the gas content (volume ratio) in the ozone ice slurry is preferably 7 to 42% by volume, more preferably 20 to 33% by volume, and particularly preferably 22 to 28% by volume. . When the gas content (volume ratio) of the ozone ice slurry is 6% by volume or less, the gas content (ozone concentration) in the ozone ice slurry is not sufficient, and the desired sterilization / deodorization effect by the ozone ice slurry is effective. There is a problem that even if only a large amount of expensive ozone ice slurry is used for a short period of time, it still cannot maintain sufficient sterilization and deodorization as well as sufficient cooling during transport and storage of fresh food. In addition, since the gas content (ozone concentration) in the ozone ice slurry is not sufficient, it is extremely difficult to mix and use it with ordinary inexpensive ice slurry. There is a problem that the cost required for refrigeration and sterilization / deodorization during storage and transportation of fresh food becomes very high. As a result, transportation and storage efficiency (including cost) as a whole decreases, and it cannot be said that sufficient contribution to the food distribution system can be brought about. On the other hand, the upper limit of the gas content (volume ratio) in the ozone ice slurry is not limited, and even if it is in a range exceeding 45% by volume, the utility value of the present invention is further improved as long as the effects of the present invention are not impaired. It will be expensive. That is, it is extremely effective in that the ozone concentration increases as the gas content increases. On the other hand, in ozone ice slurry with a high gas content, the proportion of ozone ice slurry in the unit volume is relatively decreased, and the cooling time tends to decrease, and weigh both merits and demerits, What is necessary is just to determine the gas content rate (volume ratio) of the optimal ozone ice slurry suitably. In addition, by using the manufacturing method and manufacturing apparatus of the present invention, it is possible to sufficiently ice the ozone ice slurry having a higher value in which the gas content (volume ratio) of the ozone ice slurry exceeds 45% by volume. As shown in FIG. 12A, as compared with the bubble content of 28% by volume when the cooling surface angle 3 is 0 ° and 22% by volume when the angle is 10 °, a voltage applied to the cooling member as shown in FIG. .5 times or more (28 x 1.5 = 42 vol% or more, 22 x 1.5 = 33 vol% or more) of gas can be contained, and ice making time and cooling temperature during ice making should be adjusted. A higher bubble content can be obtained. Furthermore, it is possible to further increase the ozone concentration in the gas by removing chlorine from the tap water and reusing the vaporized gas.

(2) Additive of ozone ice slurry and its concentration The ozone ice slurry of the present invention is an additive that can be made into ozone ice slurry such as propylene glycol or ethanol or salt water of a predetermined concentration, exceeding 0 vol% to 25 vol%. What is contained can be used. In particular, by using propylene glycol (PG) or ethanol (EtOH), which is a food additive, or salt water with a predetermined concentration for ozone ice slurry (solution), the refrigeration temperature is controlled by adjusting the concentration of the additive. it can. In particular, it can be controlled under a refrigeration temperature range lower than the ice refrigeration temperature (0 ° C.), and is excellent in that food can be refrigerated. The additive concentration of the additive is not particularly limited as long as it does not impair the effects of the present invention. Preferably it is 5 volume% or more, More preferably, it is 10-15 volume%, More preferably, it is the range of 20-25 volume%. If the additive concentration of the additive is 25% by volume, the food can be refrigerated in a wide temperature range up to about −18 ° C. necessary for normal food refrigeration. In addition, when refrigerated to about -18 ° C, such foods can be cooled to such a low temperature that water and fats and oils can freeze and solidify, suppressing the activity of microorganisms, and for a long time (according to the Japan Frozen Food Association, -18 ° C). If it is below, it can be preserved for about one year after production), which is excellent in that long-term transportation and preservation can be realized.

(3) Ozone ice slurry formed by ice scraping or scraping from ozone ice The ozone ice slurry of the present embodiment is obtained from (a) a harvest from ozone ice having the above-mentioned high ice gas content of the present invention. The ice peeled off by the method is scraped off using an ice scraper to generate ozone ice slurry, or the ice scraper is scraped off using an ice scraper to generate ozone ice slurry. It may be a thing. The detailed manufacturing method will be described later, but in any method, the ozone ice slurry can be generated by scraping or scraping the generated ozone ice (including dissolved ozone and ozone bubbles). Therefore, it is excellent in that it can be produced easily, does not contain any additive, does not require the cost of the additive, and becomes water after dissolution, so that no post-treatment (cleaning, recovery, etc.) is required.

(4) Use Application The use application of the ozone ice slurry having a high ice gas content of the present invention or the above mixed ice slurry is mainly for a cold preservation effect and a sterilization / deodorization action for maintaining the freshness of fresh food. The ozone ice slurry having a high ice gas content and the mixed ice slurry of the present invention have good fluidity, good heat load followability, and can spread the ozone ice slurry to fresh fish without any gaps. The fresh food that can use the ozone ice slurry is not particularly limited, and can be directly applied to, for example, fresh fish shellfish, fresh vegetables and fruits (particularly thick cucumbers, tomatoes, watermelons, melons, etc.) If the skin is not thick, use it with a gas (especially ozone gas) permeable film to prevent vegetables and fruits (eg, leafy vegetables, peaches and persimmons) from getting wet and susceptible to pain. In this case, only the ozone gas contained in the bubbles of the ozone ice slurry will work effectively.), Raw meat (again, prevent raw meat such as beef from getting wet and watery) For the purpose, it should be used by packaging with gas (especially ozone gas) permeable film (wrap film), etc. Also in this case, only ozone gas contained in bubbles of ozone ice slurry works effectively. It would be.), And the like.

  In addition, the ozone ice slurry is excellent in that it can be transported at a remote location (manufacturing location and usage location) because it can be pumped.

(5) Manufacturing apparatus and manufacturing method to be used Further, the high bubble-containing ozone ice or ozone ice slurry of the present invention uses the manufacturing apparatus shown below, and uses the manufacturing method shown below to make ice making or ice making slurry. Bubble-containing ozone ice or ozone ice slurry obtained by the above-mentioned process, wherein the bubble content (volume ratio) of the ozone ice or ozone ice slurry is higher than 6% by volume. The manufacturing apparatus and manufacturing method will be described below.

[II] Ozone ice production apparatus The ozone ice production apparatus of the present invention comprises an ozone raw material part,
An ozone generator for generating ozone from the ozone material supplied from the ozone material part;
A microbubble mixing device for generating microbubble mixed water from ozone-containing gas (oxygen + ozone) generated by the ozone generator and ozone water circulated from a water tank and / or water supplied from the outside;
In order to be able to capture microbubbles under the cooling surface (ice-making surface) of the cooling member, a pipe tip for supplying microbubble mixed water generated by the microbubble mixing device and the cooling member are inside the tank. A placed aquarium,
A refrigerant circulation device (cooling device) that circulates the refrigerant in a circulation flow path inside the cooling member so as to cool at least the cooling surface of the cooling member;
An exhaust pipe and / or the microbubble for exhausting the component (ozone + oxygen) gasified by floating microbubbles in the water mixed with microbubbles supplied into the water tank and floating on the liquid surface out of the system A supply pipe for supplying a component (ozone + oxygen) gasified by floating microbubbles in the mixed water from the water tank to the ozone generator;
It is characterized by having.

  The ozone ice production apparatus according to the present invention does not require a container for pressurization, and thus it is possible to develop an ozone ice generation apparatus that can be downsized and highly efficient. Furthermore, since the ozone ice production apparatus proposed by the present invention is not easily affected by gas solubility, any gas can be enclosed in the ice and can be expected to be used in other applications.

  Hereinafter, representative embodiments of the ozone ice production apparatus of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view schematically showing a typical embodiment of an apparatus for producing ozone ice according to the present invention, and is an apparatus provided with a flat plate-like cooling member as a cooling member. In the following, the ozone ice manufacturing apparatus of the present embodiment in FIG. 1 will be described in detail with a focus on main components.

(1) Ozone raw material part 11
As shown in FIG. 1, the ozone ice manufacturing apparatus 10 of the present embodiment first has an ozone material part 11.

  Here, in the present invention, the ozone raw material portion 11 is not particularly limited, and, for example, according to the ozone gas generation method of the ozone generator 15, for example, a discharge type (using oxygen; example of FIG. 1), In the case of the ultraviolet lamp type, an oxygen storage unit such as an oxygen cylinder (example of FIG. 1) or an oxygen production apparatus can be used. The oxygen production apparatus is not particularly limited, and is generated by, for example, an oxygen separation / recovery apparatus including an oxygen permeable membrane that selectively permeates only oxygen from an oxygen-containing gas such as air, or water electrolysis. An oxygen generator using oxygen or the like can be used. Although it is convenient to use an oxygen cylinder that is relatively inexpensive and can save space, an appropriate oxygen production apparatus may be used for continuous mass production.

  When the ozone gas generation method of the ozone generator 15 is an electrolytic method, a water storage unit such as a water storage tank or tap water (tap water) can be used as the ozone generation raw material unit 11.

(2) Ozone generator 15
Next, in the ozone ice manufacturing apparatus 10 of the present embodiment, ozone that generates ozone from an ozone raw material (oxygen) supplied through a pipe 13 from an oxygen storage part (oxygen cylinder) that is one kind of the ozone raw material part 11. A generator 15 is included.

  Here, the pipe 13 is not particularly limited. For example, when a high-pressure oxygen cylinder is used for the oxygen storage part that is the ozone raw material part 11, the pressure resistance is excellent, and at least the inner surface of the pipe is inert to ozone and oxygen. It is desirable to use materials. In addition, when using a water storage part or tap water for the ozone raw material part 11, it does not restrict | limit in particular, You may use various resin-made (for example, vinyl chloride) piping etc. which are lightweight and excellent in corrosion resistance. Any of metal pipes (made of SUS) having excellent corrosion resistance and strength can be used.

  Depending on the intended use, the ozone raw material portion 11 is set to the atmospheric atmosphere = air (oxygen-containing gas), and air (oxygen-containing gas) is supplied to the ozone generator 15 as it is without passing through the pipe 13 to generate ozone. May be. The ozone ice manufacturing apparatus 10 of the present embodiment can have a gas content (about 5 to 10 times) that is extremely high compared to existing manufacturing apparatuses. As a result, even if ozone is generated from oxygen in the air, the intended purpose can be achieved.

  The ozone generator 15 is not particularly limited, and can be roughly classified into ozone gas generation methods, and any of a discharge type (using oxygen), an electrolytic type (using water), and an ultraviolet lamp type can be used. Good. In addition, various types of ozone generators already available on the market can be used, and may be determined as appropriate according to the intended use and the amount of ozone generated.

  The ozone concentration (amount of ozone generated) in the ozone-containing gas (= ozone + oxygen) generated by the ozone generator 15 varies depending on the type (method), performance, and use conditions of the ozone generator 15, but the supplied oxygen The volume is about 2.5% by volume, 5.0% by volume, and 7.5% by volume (product catalog values). In the following various experiments, the ozone concentration in the ozone-containing gas generated by the ozone generator 15 was performed using an apparatus having 7.5% by volume (product catalog value) with respect to the supplied oxygen. However, in the apparatus 10 of this embodiment, the component (ozone + oxygen) gasified by the microbubbles in the microbubble-mixed water may be supplied (reused) from the water tank 33 to the ozone generator 15 through the pipe 39. In such a case, ozone gas having a concentration higher than the ozone concentration described above can be generated.

(3) Microbubble mixing device 23
Next, in the ozone ice manufacturing apparatus 10 of the present embodiment, ozone-containing gas (= ozone + oxygen) supplied from the ozone generator 15 through the pipe 17 and supplied (circulated) from the water tank 33 through the pipe 19. A microbubble mixing device 23 for generating microbubble mixed water from ozone water and / or water supplied from the outside through the pipe 21 is provided.

  Here, the microbubble mixing device 23 is not particularly limited. For example, as a microbubble generation method, a pressure dissolution method (example of FIG. 1), a gas-liquid mixing shear method, a method using ultrasonic waves is used. An apparatus utilizing a system utilizing SPG (shirasu porous), etc., may be mentioned, but is not limited to these. As shown in an experimental example to be described later, as the microbubble mixing device 23, there is no significant difference in the characteristics of the microbubbles between the case where the pressure dissolution type is used and the case where the gas-liquid mixing shear type is used. A sufficiently similar result can be obtained by the mixed shearing method. Further, in the gas-liquid mixed shearing method, it is considered that the microbubbles 29 are more easily charged by static electricity generated by the shearing, and therefore, it is more effective in increasing the ratio of the microbubbles 29 by applying a voltage. Are better.

  By using these microbubble mixing devices 23, the solubility of ozone in water varies depending on the device configuration, conditions, and the like. However, when the device configuration of the present embodiment is taken into consideration, it is obtained by the device 10 of the present embodiment. It can be said that the ozone concentration (solubility) of ozone water (water mixed with microbubbles) is a saturated concentration.

  Further, the ozone concentration (average value) in the microbubbles in the microbubble-mixed water obtained by the pressurized dissolution type apparatus (example of FIG. 1) which is the microbubble mixing apparatus 23 will be described in the manufacturing method described later.

  The content (mixing) of microbubbles 29 in the microbubble-mixed water obtained by the pressure dissolution type apparatus (example of FIG. 1) which is the microbubble mixing apparatus 23 will also be described in the manufacturing method described later.

  Moreover, the distribution of the microbubble diameter in the microbubble mixed water obtained by the pressure dissolution type apparatus (example of FIG. 1) which is the microbubble mixing apparatus 23 is in the range of 10 μm to 100 μm (product catalog value and actual measurement location). . As a method of measuring the microbubble diameter and its average value, a laser diffraction scattering method or the like can be used. However, microbubbles in water are very difficult to measure because particles are bonded and united over time. In the present invention, the catalog value (calculation method) of a commercially available microbubble measuring device is used. ) Based on actual measurements.

  That is, in the present invention, the microbubble diameter in the microbubble mixed water produced by the microbubble mixing apparatus is 10 to 100 μm, preferably 10 to 50 μm, more preferably 10 to 30 μm. The average value is preferably 10 to 30 μm, more preferably 15 to 25 μm, and particularly preferably about 20 μm. When the microbubble diameter is larger than the range of 100 μm, the size of bubbles taken into ozone ice during ice making becomes too large, and large bubbles can be blown when performing cold storage, sterilization, and deodorization, so a large amount of ozone gas Will be released to the atmosphere. Therefore, there is a possibility that long-term cold preservation and sterilization / deodorization action due to the release effect when the microbubbles gradually flip can be difficult to obtain. On the other hand, it is difficult in terms of device performance to make the microbubble diameter smaller than 10 μm. However, within the range that does not impair the effects of the present invention, even if the microbubble diameter in the microbubble mixed water and the average value thereof are out of the above range, they can be included in the technical scope of the present invention. .

  The piping 17 is not particularly limited, and a material inert to oxygen + ozone may be used, and a general resin piping or the like can be used. The piping 19 is not particularly limited, and a material that is inert to ozone water may be used, and a general resin piping or the like can be used. Furthermore, the pipe 21 is not particularly limited, and a material that is inert to water, for example, tap water, may be used, and a general resin pipe or the like can be used.

  The ozone water supplied from the water tank 33 through the pipe 19 and / or the water supplied from the outside through the pipe 21 is the amount of water taken out as ozone ice 39 periodically when the apparatus is operated continuously. This is because the appropriate water needs to be supplied from the outside through the pipe 21. On the other hand, during the ice making of the ozone ice 39, since the ice making device (for example, the refrigerant circulation device 37) is operated from the state where the water tank 33 is filled with a necessary amount of water, it is not necessary to replenish water from the outside. It is desirable that ozone water is supplied from the water tank 33 through the pipe 19 and circulated. This is because the ozone half-life is sufficient in water as described above, and when the production time of one ozone ice is 40 minutes (see Examples), the ozone water 31 in the water tank 33 is used without such circulation. When the ozone ice 39 is produced, the ozone in the ozone water 39 is gradually decomposed and the ozone concentration of the ozone water 31 is lowered. Therefore, the ozone water 31 in the water tank 33 is circulated to generate new microbubble mixed water. This is because it is desirable to supply. On the other hand, regarding the ozone-containing microbubbles 29, the ozone half-life of the ozone in the gas is as long as several hours to several tens of hours, and the ozone-containing microbubbles supplemented to the cooling surface (ice-making surface, heat transfer surface) 27a of the cooling member 27. There is no need to extract 29. Therefore, as shown in FIG. 1 and FIG. 2A2 to FIG. 2G2, ozone water 31 in which the ozone-containing microbubbles 29 are not mixed from the lower part of the water tank 33 on the side opposite to the supply side of the microbubble-mixed water (the farthest position). In order to be extracted and regenerated, it is preferably supplied to the microbubble mixing device 23, regenerated to saturated ozone water (microbubble mixed water), and returned to the water tank 33. In addition, the half-life of ozone dissolved in the ozone ice 39 is longer than the half-life of ozone in the ozone water 31, and by incorporating it into the ozone ice 39, it is possible to develop a cold storage and sterilization / deodorization effect for a long time. I can say something.

(3a) Chlorine removal device 47
In the ozone ice manufacturing apparatus 10 of the present embodiment, chlorine is supplied on the path of the pipe 19 for supplying water circulated from the water tank 33 to the microbubble mixing apparatus 23 and / or on the path of the pipe 21 for supplying water from the outside. It is desirable to install a removing device 47. In FIG. 1, the example which provided the chlorine removal apparatus 47 on the path | route of the piping 21 is shown.

  The chlorine removing device 47 is particularly effective when the ozone ice 39 is made using tap water containing chlorine. When using tap water, the cost reduction effect is large and advantageous as compared with the case where distilled water is used. Furthermore, by removing chlorine from the tap water, an effect of increasing the amount of dissolved ozone and the amount of ozone in the bubble-containing microbubbles 29, and further the amount of the microvalve 2 itself can be obtained (see FIG. 13).

  Therefore, from the beginning of the operation of the manufacturing apparatus 10 until the required amount of ozone water 31 is filled in the water tank 33, the required amount of water is supplied to the water tank 33 through the microbubble mixing device 23 through the pipe 21 path for supplying tap water from the outside. Water (ozone water) is supplied. Therefore, by installing the chlorine removing device 47 on the path of the pipe 21, chlorine can be effectively removed, and decomposition of ozone can be extremely effectively prevented by the chlorine.

  On the other hand, after the required amount of water (ozone water) is supplied to the water tank 33, the supply of tap water from the pipe 21 path is stopped, and the microbubble mixing device 23 is supplied through the pipe 19 path for supplying ozone water from the water tank 33. Is supplied with ozone water, and microbubble mixed water obtained by the mixing device 23 is supplied to the water tank 33 and circulated. At this time, only when chlorine in the tap water supplied through the pipe 21 path is not completely removed by the chlorine removing apparatus 47 on the pipe 21 path, the chlorine removing apparatus (see FIG. (Not shown) can effectively function to decompose chlorine remaining slightly in ozone water.

  The chlorine removing device 47 capable of removing chlorine in the water is not particularly limited, and a conventionally known device can be appropriately used. Specifically, an ultraviolet irradiation device, a water purification device using a hollow fiber membrane, a device filled with activated carbon or zeolite, and the like can be used. However, the present invention is not limited to these.

(4) Water tank 33
Next, in the ozone ice manufacturing apparatus 10 of the present embodiment, the microbubble mixed water generated by the microbubble mixing apparatus 23 is supplied so that the microbubbles 29 can be captured below the cooling surface 27a of the cooling member 27. A pipe tip 25a to be connected and the cooling member 27 have a water tank 33 disposed inside the tank.

  In other words, (i) a pipe 25 for supplying the microbubble mixed water generated by the microbubble mixing device 23 into the water tank 33 is provided, and the tip of the pipe 25 is a lower part in the water tank 33 and is cooled. It is arranged under the cooling surface (ice making surface) 27a below the member 27 so as to communicate (penetrate) to a position where the microbubbles 29 can be easily captured, and (ii) below the cooling surface (ice making surface) 27a below the cooling member 27. It can also be said that it has a water tank 33 in which the cooling member 27 is installed (deployed) so that the microbubbles 29 can be captured.

  Here, the pipe 25 is not particularly limited, and a material inert to ozone water may be used, and a general resin pipe or the like can be used.

  Here, below the cooling surface (ice-making surface) 27a below the cooling member 27 is directly below the cooling surface (ice-making surface) 27a below the cooling member 27 (in the initial stage of ice making), as well as FIG. 1, FIG. 2A2, FIG. 2A3, FIG. 2B2, FIG. 2C2, FIG. 2D2, FIG. 2E2, FIG. 2F2, and FIG. 2G2, ozone ice 39 is generated on the cooling surface 27a below the cooling member 27 by ice making, so that the ozone ice 39 below the cooling surface 27a is generated. The lower side (lower part or lower part) may be interposed.

  Further, the tip 25a of the bubble mixed water supply pipe 25 and the cooling member 27 are arranged inside the water tank 33 so that the microbubbles 29 can be captured under the cooling surface 27a of the cooling member 27. In the process of gradually growing (generating) the ozone ice 39 under the cooling surface 27a at the time of ice making, the microbubbles 29 are efficiently taken into the ozone ice 39, and some of the microbubbles 29 are combined (grown). This is because a large number of bubbles can be contained.

  As shown in FIGS. 1 to 2, the tip of the pipe 25 is a lower part in the water tank 33, and effectively captures the microbubbles 29 under the cooling surface (ice making surface) 27 a below the cooling member 27. It is desirable to penetrate (communicate) to an easy position. With this configuration, the microbubbles 29 are effective under the ice making surface (cooling surface) 27a below the cooling member 27 while floating (floating) along the flow of the microbubble mixed water supplied from the tip of the pipe 25 ( This is because it can be captured in a large amount (see FIG. 10). Accordingly, the front end of the pipe 25 can be adjusted appropriately so that it can be appropriately adjusted according to the flow rate (flow rate) of the water mixed with microbubbles, the size of the water tank, the structure and arrangement of the cooling member, and the like. It is desirable to have a structure that can be stretched and bent and stretched vertically and horizontally.

  In addition, the supply of microbubble mixed water into the water tank 33 can be performed continuously or intermittently (this point will be described in the manufacturing method and the embodiment) at an appropriate position on the pipe 25. Various valves (not shown) and pumps (not shown) such as opening / closing valves or flow rate adjusting valves, and a control mechanism provided with various sensors, measurement units and control units necessary for controlling them (system) (system) ( Neither of them may be provided). It should be noted that various valves (not shown) and pumps (not shown) such as on-off valves or flow rate adjusting valves to appropriate positions on these pipes, various sensors and measuring units necessary for controlling these, and Installation of a control mechanism (system) (not shown) provided with a control unit is also installed in other pipes, water tanks, various devices, etc., and the control mechanism (system) of the entire device is constructed. This is effective in increasing the size and industrialization (commercialization).

  As shown in FIGS. 1, 2A2, 2A3, 2B2, 2C2, 2D2, 2E2, 2F2, and 2G2, the water tank 33 includes an ice making surface (cooling surface) 27a below the cooling member 27. The cooling member 27 is provided so as to capture the microbubbles 29. Further, the cooling member 27 is arranged as shown in FIGS. 1, 2A2, 2A3, 2B2, 2C2, 2D2, 2E2, 2F2, 2G2, and the cooling surface of the cooling member 27 is in the water tank 33. What is necessary is just to arrange | position so that it may become below the liquid level.

  Here, the water tank 33 is preferably a sealed water tank having a lid 33a that can be opened and closed or detached. However, there is no particular limitation as long as the function and effect of the present invention are not impaired, such as using an open (open) water tank.

  In order to store the required amount of ozone water 31 in the water tank 33 before the start of ice making, ozone water may be supplied in advance from the outside, but it is desirable to store it using the manufacturing apparatus 10. For example, the ozone raw material part 11, the ozone generator 15 that generates ozone from the raw material supplied from the ozone raw material part 11, the ozone-containing gas generated by the ozone generator 15, and the water supplied from the outside Therefore, it is desirable to use the microbubble mixing device 23 that generates the microbubble mixed water to supply the microbubble mixed water to the water tank 33 and secure the necessary amount of ozone water 31 and at the same time proceed with the preparation of ice making. I can say that. When the required amount of ozone water is secured, ozone water is supplied from the water tank 33 to the microbubble mixing device 23 as described above, and the obtained microbubble mixed water is supplied (circulated and regenerated) to the water tank 33. Is desirable.

(5) Cooling member 27
In the water tank 33, the flat cooling member 27 is horizontal (parallel to the horizontal liquid surface) so as to capture the microbubbles 29 under the ice making surface (cooling surface = heat transfer surface) 27 a below the cooling member. ).

  However, in the present invention, the shape, cooling surface angle, material, and the like of the cooling member 27 are not particularly limited as long as the effects of the present invention are not impaired. It can be installed.

(A) Shape of the cooling member 27 (of the heat transfer surface) As a shape of the cooling member 27, in addition to a rectangular (rectangular) flat plate shape (FIG. 2A1), an arbitrary square shape such as a triangle, a rhombus, a pentagon, a hexagon, etc. From the surface of a sphere such as a flat plate shape (both downward cooling), circular, elliptical, etc. (all down cooling), corrugated plate (down cooling), hemispherical (FIG. 2B1) to ½ the diameter An upper sphere (FIG. 2C1) (both cooled downward), a semi-cylindrical shape (FIG. 2G1), a cylindrical shape (FIG. 2D1), and a cylinder with an arbitrary angle such as a triangle or a square. However, it is not limited to these. For example, the effect of the present invention, such as the shape of a triangular roof as shown in FIG. 2E1 (the shape obtained by folding a flat plate into two so that the side faces are triangular), and the shape of a curved flat plate as shown in FIG. 2F1 As long as the microbubbles can be captured under the cooling surface of the cooling member, any shape may be used.

  FIG. 2 shows some specific examples of the shape of the cooling member 27 of the present invention. That is, FIG. 2 is a schematic view schematically showing a typical embodiment of the cooling member used in the present invention.

  Among these, FIG. 2A1 is a schematic view of a flat cooling member 27a. FIG. 2A2 is a schematic diagram showing a state in which the water tank 33 is provided with the flat cooling member 27a horizontally (cooling surface angle of the cooling member: 0 °; cooling downward). FIG. 2A3 is a schematic diagram showing a state in which the water tank 33 is provided with a cooling surface angle of 10 ° (downward cooling) of the flat plate-like cooling member 27a.

  FIG. 2B1 is a schematic view of a hemispherical cooling member 27b. FIG. 2B2 is a schematic diagram showing a state in which the water tank 33 is provided with the hemispherical cooling member 27b so that the spherical cut surface is a horizontal bottom surface (downward cooling, ice is generated inside).

  FIG. 2C1 is a schematic view of an upper spherical cooling member 27c cut horizontally from the surface of the sphere at a depth of 1/3 of the diameter. FIG. 2C2 is a schematic diagram illustrating a state in which the upper sphere-shaped cooling member 27c is provided in the water tank 33 so that the sphere cut surface is a horizontal bottom surface (downward cooling, generating ice inside).

  FIG. 2D1 is a schematic view of a cylindrical cooling member 27d. FIG. 2D2 includes the cylindrical cooling member 27d provided in the water tank 33 so that the cylindrical cooling member 27d faces sideways (the cylindrical central axis is parallel: ice is generated inside). It is the schematic showing a state. However, in any of the cooling members, illustration of the refrigerant flow path therein is omitted.

  FIG. 2E1 is a schematic view of a cooling member having a triangular roof shape (a shape in which a flat plate is folded in half so that the side faces are triangular), and FIG. 2E2 is a (folding the flat plate in half so that the side faces are triangular). It is the schematic showing the state equipped with the cooling member of the shape formed in the water tank so that the top part of a triangular roof may become the upper part (downward cooling; ice is produced | generated inside).

  FIG. 2F1 is a schematic view of a curved flat plate cooling member 27d, and FIG. 2F2 is an inverted U-shaped curved plate (downward cooling, generating ice on the inside). It is the schematic showing the state provided in the water tank 33.

  FIG. 2G1 is a schematic view of a semi-cylindrical cooling member 27d. FIG. 2G2 shows the semi-cylindrical cooling member 27d facing sideways (the lateral end surface is an inverted U-shape and the semicylindrical central axis is parallel; downward cooling, inner It is the schematic showing the state with which the water tank 33 was equipped so that it might become ice. However, any cooling member 27 in FIGS. 2A1 to 2G1 does not show the refrigerant flow path inside.

(B) Cooling surface angle of the flat cooling member 27 (heat transfer surface posture)
Further, the cooling surface angle of the cooling member 27 of the present invention is not particularly limited as long as it does not impair the effects of the present invention, and can be installed at an arbitrary angle.

  FIG. 3A shows cooling as a cooling member in which a flat cooling member is horizontal (cooling surface angle is 0 ° = horizontal wall) and the cooling member is vertical (cooling surface angle is 90 ° = vertical wall). It is drawing (graph) showing the mode of the bubble content rate (volume%) in ice when changing a cooling surface angle (degree) to a member. FIG. 3B is a drawing (graph) showing the relationship between the bubble capture rate (%) of ice when the cooling surface angle in FIG. 3A is 0 ° (horizontal wall) and 90 ° (vertical wall).

  FIG. 4A is a drawing showing a photograph of an ice plane (surface) generated from above when the cooling surface angle of the cooling member of FIG. 3A is 0 ° (horizontal wall). 4B is a drawing showing a photograph of the side cross section (transverse cross section) of the ice of FIG. 4A taken from the side. Here, the upper part of the drawing of FIG. 4B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 5A is a drawing showing a photograph of an ice plane (surface) generated from the upper side with a cooling surface angle of 10 ° of the cooling member of FIG. 3A taken from above. 4B is a drawing showing a photograph taken from the side of the ice of FIG. 4A. Here, the upper part of FIG. 5A is the lower side when tilted by 10 °, and the lower part of the drawing is the upper side when tilted by 10 °. The upper part of the drawing in FIG. 5B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 6A is a drawing showing a photograph of the ice plane (surface) generated from the upper side with a cooling surface angle of 15 ° of the cooling member of FIG. 3A taken from above. 6B is a drawing showing a photograph taken from the side of the ice of FIG. 6A. Here, the upper part of FIG. 6A is the lower side when tilted by 15 °, and the lower part of the drawing is the upper side when tilted by 15 °. The upper part of the drawing in FIG. 6B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 7A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with a cooling surface angle of 20 ° of the cooling member of FIG. 3A. FIG. 7B is a drawing showing a photograph taken from the side of the ice of FIG. 7A. Here, the upper part of FIG. 7A is the lower side when tilted by 20 °, and the lower part of the drawing is the upper side when tilted by 20 °. The upper part of the drawing of FIG. 7B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 8A is a drawing showing a photograph of a plane (surface) of ice generated from the upper side with a cooling surface angle of 25 ° of the cooling member of FIG. 3A taken from above. FIG. 8B is a drawing showing a photograph taken from the side of the ice of FIG. 8A. Here, the upper part of the drawing in FIG. 8A is the lower side when tilted by 25 °, and the lower part of the drawing is the upper side when tilted by 25 °. The upper part of the drawing in FIG. 8B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 9A is a drawing showing a photograph of an ice plane (surface) generated from the upper side with a cooling surface angle of 30 ° of the cooling member in FIG. 3A taken from above. FIG. 9B shows a photograph taken from the side of the ice of FIG. 9A. Here, the upper part of FIG. 9A is the lower side when tilted by 30 °, and the lower part of the drawing is the upper side when tilted by 30 °. The upper part of the drawing of FIG. 9B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 10A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with a cooling surface angle of 45 ° of the cooling member of FIG. 3A. FIG. 10B shows a photograph taken from the side of the ice in FIG. 10A. Here, the upper part of FIG. 10A is the lower side when tilted by 45 °, and the lower part of the drawing is the upper side when tilted by 45 °. The upper part of the drawing of FIG. 10B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  FIG. 11A is a drawing showing a photograph taken from above of a flat surface (surface) of ice generated with a cooling surface angle of 90 ° of the cooling member of FIG. 3A. FIG. 11B is a drawing showing a photograph taken from the side of the ice of FIG. 11A. Here, the upper part of FIG. 11A is the lower side when tilted by 90 °, and the lower part of the drawing is the upper side when tilted by 90 °. The upper part of the drawing in FIG. 11B is the surface side, and the lower part of the drawing is the cooling surface (ice making surface) side.

  From FIG. 1 to FIG. 11 (particularly FIG. 3), the cooling surface angle (heat transfer surface posture) of the flat cooling member 27 of the present invention is preferably 0 ° (horizontal) to 60 °, preferably 0 ° to It is in the range of 45 °, more preferably 10 to 45 °, particularly preferably 10 to 15 °. FIG. 3A shows that the bubble content (volume%) decreases as the cooling surface angle increases. When the cooling surface angle is 0 °, the bubble content is about 28% by volume, whereas when the cooling surface angle is 90 °, the bubble content is about 7% by volume. Here, the cooling surface angle refers to an angle formed by a flat surface (horizontal plane) and a cooling surface 27a of the flat plate-like cooling member 27 as shown in FIGS. Specifically, as shown in FIG. 2A2, when the angle formed by the plane (horizontal plane) and the horizontal cooling surface 27a is 0 °, the cooling surface angle is 0 °. As shown in FIG. 2A3, when the angle formed by the plane (horizontal plane) and the cooling surface 27a is 20 °, the cooling surface angle is 20 °. As shown in FIG. 2A4, when the angle formed by the plane (horizontal plane) and the vertical cooling surface 27a is 90 °, the cooling surface angle is 90 °. In the case of a shape other than the flat plate-like cooling member 27, for example, the cooling member 27 in FIGS. 2B to 2G is arranged so that most of the cooling surface 27a is in an angle range of 0 ° (horizontal) to 60 °. However, there is no particular limitation as long as it can capture microbubbles below (in the vicinity of) the cooling surface 27a even if it is outside the above range.

  However, looking at the photograph (drawing) of ice with a cooling surface angle of 0 ° in FIG. 4, there is a large hole on the surface, and the measurement result of the bubble content (volume%) has increased due to the influence of the hole. Seem. However, when the cooling surface angle is gradually inclined, as shown in FIGS. 5 to 8, large holes on the surface tend to gradually decrease.

  When the tendency is observed in detail, when the cooling surface angle is 10 to 15 °, the bubble content rate is greatly increased as compared with the case where the cooling surface angle is 20 ° (see FIG. 3). When the cooling surface angle is 20 to 45 °, the bubble content is hardly changed. When the cooling surface angle is 90 °, the bubble content is reduced to about half compared to the case where the cooling surface angle is 20 to 45 °. . The white spots in ice are contained bubbles. Therefore, from FIG. 3, it can be said that the cooling surface angle is optimally 10 to 15 ° in consideration of the bubble content. The bubble content at that angle is about 22% by volume. This value is about four times as large as 6% by volume reported so far (see Patent Document 1).

  The cooling surface angle is an example in which the cooling member 27 has a flat plate shape, and in the case of other polygonal shapes such as a triangle, pentagon, and hexagon, a disc shape, a corrugated plate shape, etc., FIGS. The optimum cooling surface angle may be determined as appropriate by conducting a preliminary experiment in accordance with the experiment shown in FIG.

  In addition, in the case of an upper sphere, a cylinder, or a cylinder with an arbitrary angle such as a triangle or a square by cutting horizontally at an arbitrary depth from the surface of a sphere such as a hemisphere to 1/2 the diameter The optimum tilt angle may be determined as appropriate by changing the tilt angle of the cylindrical body with the horizontal angle of 0 °.

  In the case of an upper sphere, a cylinder, or a cylinder with an arbitrary angle such as a triangle or a square by cutting horizontally at an arbitrary depth from the surface of a sphere such as a hemisphere to 1/2 the diameter As shown in FIG. 2D2, when the cylindrical main body is installed at a horizontal angle of 0 °, the entire inside of the cylinder becomes a cooling surface (ice-making surface), so the upper side is the ozone ice 39 of the present invention, that is, ozone-containing Although it becomes the ice which has a bubble and dissolved ozone, the lower part turns into the ice 39b which does not contain an ozone containing bubble and has dissolved ozone, and does not become the ozone ice 39 of this invention.

  Accordingly, when the high bubble content ozone ice of the present invention is exclusively required, only the upper side may be used. In this case, the refrigerant flow path leading to the inside of the tubular body is tubular so that only the upper part inside the tubular body is the cooling surface (ice-making surface) and the lower part inside the tubular body is not the cooling surface (ice-making surface). You may provide only in the upper part inside a main body.

  On the other hand, when the ozone ice of the present invention is used in combination with normal ice, the ozone ice 39 of the present invention (ice having ozone-containing bubbles 29a and dissolved ozone) on the upper side, and the lower side. The ice 39b having only dissolved ozone that does not include the ozone-containing bubbles 29a may be effectively used as an alternative to ordinary ice. In this case, there is no wasted ice, and the inner and lower ozone ice 39b also has dissolved ozone, so there is a certain degree of sterilization / deodorization effect along with cold storage, and more effective sterilization / deodorization effect than using normal ice. Excellent.

(C) Material of the cooling member 27 (cooling surface = heat transfer surface side) The material of the cooling member 27 is not particularly limited, and copper, aluminum, iron, stainless steel plate (SUS), etc. can be used. is there. Among them, copper having excellent thermal conductivity and extensibility (workability) can be effectively used. This is because air bubbles are easily captured (contained) in the ice when the cooling rate is high. Therefore, copper with high thermal conductivity is preferable. However, in the case of copper, in order to prevent corrosion due to ozone, it is more desirable to apply a film having excellent thermal conductivity and ozone resistance such as electroless nickel plating. Aluminum and iron must also be plated. On the contrary, the thermal conductivity is about 1/25 compared to copper, but in the case of continuously producing SUS or the like having excellent corrosion resistance, it can be said that it is easy to use because maintenance or replacement time may be late. The entire cooling member 27 is not necessarily a member having excellent thermal conductivity. For example, in FIG. 1, only the lower half of the cooling member 27 (cooling surface = heat transfer surface side) is a member having excellent thermal conductivity. The upper half of the cooling member 27 may have a structure that enhances the cooling effect by the refrigerant as a material having excellent heat insulation properties or a material that reflects heat. Further, in order to make it easy to peel ozone ice from the cooling member 27 after ice making, a polymer film or the like having good peelability is formed as a thin film that does not affect the thermal conductivity so that the cooling surface of the cooling member 27 = heat transfer surface side. It may be coated.

  Further, in the cylindrical cooling member 27 as shown in FIG. 2D1, a structure in which the upper half cylinder 27m and the lower half cylinder 27n are combined may be used. When such a structure 27 is used, it is excellent in that the ozone ice 39 having a high bubble content of the present invention obtained by ice making and the ozone ice 39b containing dissolved ozone can be easily separated and quickly removed. Yes. Further, in terms of easily and quickly removing the obtained ozone ice 39 having a high bubble content of the present invention, the spherical member 27m on the right half and the left half on the spherical cooling member 27 in FIGS. 2B1 and 2C1. A structure in which the spherical member 27n is combined may be used. Also, the triangular roof shape cooling member 27 in FIG. 2E1 may be a structure in which a right half flat plate member 27m and a left half flat plate member 27n are combined.

(5a) Power supply device 47
The ozone ice manufacturing apparatus 10 according to this embodiment preferably further includes a power supply device 47 for applying a voltage to the cooling member 27. This is because the microbubbles generated in the present invention are charged, and the microbubbles 29 floating on the liquid surface by the voltage application to the cooling member 27 are also electrically attracted and supplemented below the cooling surface 27a. It is excellent in that it can be held in a state (the amount of bubbles under the cooling surface 27a increases).

  The power supply device 47 is not particularly limited, and a DC power supply (example of FIG. 1) can be used. Alternatively, an AC power supply may be used, or conversion from AC to DC can be performed. Rectifiers or converters to be used may be used, inverters that convert DC to AC may be used, DC-DC converters that convert DC voltage may be used, and various transformers may be used. it can.

  The voltage (preferably DC voltage) applied to the cooling member 27 is not particularly limited and may be a voltage value exceeding 0 V, preferably 50 V or more, preferably 100 V or more, more preferably 100 to 300 V, Especially preferably, it is the range of 200-300V. Depending on conditions such as the magnitude of the applied voltage, the amount of microbubbles on the cooling surface 27a of the cooling member 27 can be increased to about 30% by volume (see FIG. 12A). Further, when the flat cooling member 27 is installed horizontally, the bubble content of ice with respect to the bubble concentration in water can be increased to about 110 to 150% depending on conditions such as the magnitude of the applied voltage. On the other hand, in the example of Patent Document 1 in which the flat cooling member 27 is installed vertically, the bubble content of ice with respect to the bubble concentration in water is 30 to 60% by volume (ozone ice) depending on conditions such as the magnitude of the applied voltage. The gas content is about 6%), and the effect of voltage application to the cooling member 27 cannot be enjoyed at all (see FIG. 12B).

(6) Refrigerant circulation device (cooling device) 37
Next, in the ozone ice manufacturing apparatus 10 of the present embodiment, in order to cool at least the cooling surface 27a of the cooling member 27 using the heat conduction effect, a refrigerant (see FIG. It has a refrigerant circulation device (cooling device) 37 that circulates (not shown). However, the present invention is not limited to the above embodiment.

  Here, the refrigerant (brine; including antifreeze) is not particularly limited as long as the cooling surface 27a of the cooling member 27 described below can be cooled to the cooling temperature range shown below. Specific examples include brines such as ethylene glycol and ethanol, ammonia, carbon dioxide gas, sulfurous acid gas, alternative refrigerants, and the like, but are not limited thereto. In the solution (brine) such as chloride or ethylene glycol, the freezing temperature can be adjusted by adjusting the concentration thereof, and the cooling surface 27a of the cooling member 27 can be cooled to the cooling temperature range shown below.

  The cooling temperature of the cooling surface 27a of the cooling member 27 using the refrigerant (not shown) is in the range of −6.8 to −13 ° C., more preferably −10 to −13 ° C. When the cooling temperature is higher than −6.8 ° C., it takes a long time to make ice to a predetermined thickness, resulting in high production costs and a reduction in the amount of bubbles taken in along with a decrease in ice making speed. It is not desirable. On the other hand, the lower limit of the cooling temperature is not particularly limited, but when it is lower than −13 ° C., the usable refrigerant is limited, an expensive refrigerant is required, and the running cost is increased.

  The circulation channel 35 in the cooling member 27 has a good thermal conductivity, so that a simple U-shaped circulation channel is sufficient, or a cooling member such as a commercial or household refrigerator or air conditioner. As long as it is within a range that does not affect the function and effect of the present invention, such as a complicated wave-shaped circulation channel, the circulation channel may have any shape. Further, the circulation path 35 may be formed of a material different from that of the cooling member 27. Even in such a case, it is preferable to use a material having high thermal conductivity as the material of the circulation path 35.

  The refrigerant circulation device (cooling device) 37 is not particularly limited, and for example, a reciprocating compressor, a rotary compressor, a vibration compressor, an absorption refrigerator, a compression refrigerator, and a vapor compression type. A refrigerator or the like can be used. However, the present invention is not limited to these.

(7) Exhaust pipe 41 and / or supply pipe 43
Next, in the ozone ice manufacturing apparatus 10 of the present embodiment, the component (ozone + oxygen) in which the microbubbles 29 in the microbubble-mixed water supplied into the water tank 33 float on the liquid surface of the water tank 33 and are gasified. The exhaust pipe 41 and / or the microbubble 29 in the microbubble-mixed water floats on the liquid surface and gasifies the component (ozone + oxygen) from the water tank 33. A supply pipe 43 for supplying the ozone generator 15 is provided.

  The exhaust pipe 41 is not particularly limited, and a material inert to the gasified component (ozone + oxygen) may be used, and a general resin pipe or the like can be used. Further, the outlet of the exhaust pipe 41 is preferably installed on the upper surface side of the upper lid 33a of the water tank 33 as shown in FIG. 1, but on the side surface of the upper lid 33a (but above the liquid level). May be installed.

  Further, the exhaust pipe 41 may not be provided, and natural evacuation may be performed by setting the upper part of the water tank 33 without the upper lid 33a as an open system (opening) instead of the sealed water tank 33.

  The supply pipe 43 is not particularly limited, and a material that is inert to the gasified component (ozone + oxygen) may be used, and a general resin pipe or the like can be used. Further, the outlet of the supply pipe 43 is preferably installed on the upper surface side of the upper lid 33a of the water tank 33 as shown in FIG. 1, but on the side surface of the upper lid 33a (however, above the liquid level). May be installed.

(7a) Moisture removal means 45
Moreover, in the ozone ice manufacturing apparatus 10 of the present embodiment, water vapor (water) is contained in the component (ozone + oxygen) that the microbubbles 29 in the microbubble mixed water float and gasify on the liquid surface. There may be. In such a case, it is desirable that a moisture removing means 45 is further provided in the path of the pipe 43 for supplying the gasified component to the ozone generator 15 (particularly in the case of a discharge ozone generator). By reusing after removing moisture in the gasified component, the dissolved ozone concentration in the microbubble mixed water obtained from the ozone generator 15 through the microbubble mixing device 23, the ozone concentration in the microbubble, and the microbubble amount itself Is also excellent in that it can increase. In addition, since ozone containing moisture (humidity) in the gasified component is highly corrosive, it is desirable to remove moisture immediately after taking out from the water tank if possible before supplying it into the microbubble mixing device 23 (see FIG. (Refer to the installation position in 1).

The moisture removing unit 45 is not particularly limited, and a conventionally known moisture removing unit can be appropriately used. Preferably, as the water removing means 45, (a) a part 43a of the gasified component supply pipe 43 is provided with a detachable enlarged diameter portion 43a, and the gasified portion 43 is subjected to the gasification. It is desirable to arrange a Peltier element 45a for cooling and dehumidifying (and removing moisture) the components. Alternatively, (b) the supply pipe 43 is preferably filled with a moisture absorbent 45b such as silica gel for adsorbing and removing moisture from the gasified component. Further, as a configuration combining (a) and (b), (c) a Peltier element 45a is disposed in the enlarged diameter portion 43, and a hygroscopic agent 45b such as silica gel is disposed in the front and / or rear pipe 43. May be filled. However, the present invention is not limited to these. In addition, the moisture removing means 45 is not limited in the case of being arranged at one place, and may be installed at a plurality of places.
[IIa] Ozone Ice Slurry Manufacturing Device of First Embodiment The ozone ice slurry manufacturing device of the first embodiment of the present invention is further converted into ozone ice slurry into the ozone ice manufacturing device 10 described above in [II]. The additive storage unit 51 to be obtained, and the flow rate adjustment to supply the additive at a predetermined ratio (volume ratio) to the water supplied to the device 23 from the storage unit 51 to the microbubble mixing device 23 And a supply path (pipe) 55 provided with a device 53. In the ozone ice slurry manufacturing apparatus having such a configuration, by making the ozone ice 39 into an aqueous solution, the liquid temperature can be lowered and the ozone solubility can be increased. Moreover, the ozone ice slurry (39a) has fluidity and good thermal load followability. Therefore, the ozone ice slurry (39a) can be filled (supplied) along the shape of fresh fish or the like without any gaps, and the cold-retaining property and the sterilizing / deodorizing effect can be significantly improved. In addition, the ozone ice slurry (39a) can be provided in a temperature range suitable for the optimum storage or transportation temperature of the produced food, and the freshness retention effect of the produced food is remarkably enhanced and stable for a long time. And freshness can be maintained. Further, if necessary, when the fresh food is stored in quick freezing (−18 ° C. or lower) and kept fresh, the heat load followability is good. For example, the additive is a kind of food additive. When propylene glycol (PG) is used, an ozone ice slurry (39a) that can be refrigerated in a temperature range of −18 ° C. or lower can be provided by setting the initial concentration of PG to 25% by volume or more.

(1) Storage unit 51
The ozone ice slurry manufacturing apparatus 10 </ b> A of the present embodiment includes an additive storage unit 51 that can slurry ozone ice.

  The storage unit 51 is not particularly limited as long as it can store the additive capable of slurrying ozone ice in an appropriate ratio so as to be supplied to the microbubble mixing device 51. When salt water is used, it is desirable to use a material (for example, stainless steel (SUS304)) having corrosion resistance against salt water.

(A) Additive The additive is not particularly limited as long as it can be formed into an ozone ice slurry. For example, propylene glycol (PG) or ethanol or salt water having a predetermined concentration (preferably an ozone ice slurry). The salinity is adjusted to the salinity in seawater). However, it is not limited to these.

  PG or ethanol, which are the additives exemplified above, or salt water of a predetermined concentration are all food additives, and even when they are taken into ozone ice slurry, they can be used for storing fresh foods, etc. It can be used without problems. Two or more of the above additives may be used in appropriate combination.

  Further, the refrigeration temperature (ozone ice slurry temperature) can be controlled by adjusting the concentration of the additive. For example, by adjusting the initial concentration of PG to 5% by volume, it is possible to produce an ozone ice slurry that can be refrigerated in the temperature range of about -4 ° C. As the PG concentration is increased, refrigeration at a lower temperature is possible. A simple ozone ice slurry can be produced. For example, by adjusting the initial concentration of PG to 25% by volume, it is possible to produce an ozone ice slurry that can be refrigerated (refrigerated) in a temperature range of about −18 ° C. that can be frozen.

  In addition, the ozone ice slurry using salt water of a predetermined concentration is particularly suitable for maintaining the freshness of marine fish and shellfish by adjusting the concentration of seawater when the ice slurry is turned into an aqueous solution. In addition, ozone ice slurry using salt water is superior in that it has a low temperature holding performance superior to that of fresh water ice. Furthermore, by using an ozone ice slurry, the fluidity increases as described above, and high-density heat transport becomes possible. Moreover, since the contact area with respect to one fish becomes large, a fish can be cooled uniformly and rapidly. Thus, it can be said that the ozone ice slurry using salt water is suitable for maintaining the freshness of fish. In particular, deep ocean water is superior in that it has less spoilage bacteria than surface water and can produce ozone ice slurry using salt water that is hygienic. Moreover, the temperature of deep ocean water is 8-10 ° C throughout the year, and the surface water is 16-25 ° C. The temperature difference is large, and it is also excellent in that ice can be made with a small amount of electric power when ice is produced. .

  As described above, it is difficult to uniquely define the additive concentration, and within the range that does not impair the operational effects of the present invention, the characteristics of each additive described above are used and optimum for each application. It may be used by adjusting to a suitable concentration. It can be said that the optimum concentration for each application is desirably obtained in advance by conducting a preliminary experiment or the like.

(2) Supply path (pipe) 55 provided with the flow rate adjusting device 53
In the apparatus 10 of the present invention, the supply provided with the flow rate adjusting device 53 to supply the additive at a predetermined ratio to the water supplied to the device 23 from the storage unit 51 to the microbubble mixing device 23. A path (pipe) 55 is provided.

  The flow rate adjusting device 53 is not particularly limited, and examples thereof include a flow rate adjusting valve, but are not limited thereto.

The supply path (pipe) 55 is not particularly limited, and a material having corrosion resistance may be appropriately selected and used depending on the type of additive. In addition, the supply of the additive to the microbubble mixing device 23 is quickly performed while water (tap water) is supplied from the outside through the pipe 21 at the initial stage of slurry preparation so that the water has a predetermined concentration. It is desirable to carry out (complete), and then the additive-containing ozone water adjusted to a predetermined concentration supplied from the water tank 33 storing the required amount of ozone water through the pipe 19 is further supplied with an additive. It is suitable for ice making of a homogeneous ozone ice slurry to adjust so that it may not be necessary. However, in the case of an additive that easily gasifies together with the microbubbles 29 during the production of ethanol or the like, the amount of reduction due to gasification is timely and appropriate for the additive-containing ozone water adjusted to a predetermined concentration supplied through the pipe 19. You may make it supply an additive.
[IIb] Ozone Ice Slurry Manufacturing Device of Second Embodiment The ozone ice slurry manufacturing device of the second embodiment of the present invention is the same as the ozone ice manufacturing device 10 described in [II] above, but further cooling of the cooling member 27. The ozone ice 39 generated on the surface 27a is provided with (a) an ice scraping device that scrapes off the ice peeled off by the harvest method, or (b) a device (not shown) that scrapes off the ice by the scraping method. It is characterized by this.

  The heat medium peeling method (harvest method) is a method of peeling ozone ice from the cooling surface 27a of the cooling member 27 by replacing the refrigerant circulating in the cooling member 27 with a heat medium.

  The ice shaving apparatus that scrapes off the ice peeled off by the heat medium peeling method (harvest method) is not particularly declared, and includes, for example, an ice shaving machine, a cutter, and a blade (all of which are flat plate cooling members 27). Effective for scraping off the ozone ice 39 generated on the cooling surface 27a) and a rotor (effective for scraping off the ozone ice generated on the cooling surface 27a of the cylindrical cooling member 27). There are no restrictions.

A scraping device, such as a rotating blade, a rod having blades, or a rotating body such as a screw called an auger (to scrape ozone ice generated on the cooling surface 27a of the cylindrical cooling member 27). Effective) and the like, but are not limited thereto.
[III] Method for Producing Ozone Ice The method for producing ozone ice of the present invention is a method for producing desired ozone ice using the above-mentioned [II] device for producing ozone ice of the present invention. For this reason, the apparatus configuration (and part of the manufacturing conditions) used in this manufacturing method has already been described in detail in the above [II], and thus description thereof is omitted here.

The method for producing ozone ice of the present invention includes an ozone generation stage in which ozone is generated by an ozone generator from a raw material supplied from an ozone raw material part,
Bubble-containing water generation in which the ozone-containing gas generated in the ozone generation stage and water supplied from a water tank and / or water supplied from the outside are introduced into a micro-bubble mixing device to generate micro-bubble mixed water Stages,
The tip of the bubbled water supply pipe and the cooling member are arranged so that the microbubble mixed water generated in the bubble mixed water generation step can be captured by the microbubbles below the cooling surface of the cooling member. A bubble-mixed water supply stage for supplying to a water tank arranged inside the tank;
In the state where the microbubbles are captured on the cooling surface side of the cooling member by the bubble mixed water supply step, the refrigerant is circulated from the refrigerant circulation device to the circulation flow path inside the cooling member, and at least the cooling surface of the cooling member is An ozone ice generation stage for cooling and generating ozone ice containing bubbles on the cooling surface side;
During the ozone ice generation step, an exhausting process for exhausting the components gasified by the microbubbles in the bubble-containing water supplied into the water tank out of the system from the water tank, and / or the bubbles in the bubble-containing water are gasses. A step of reusing the gasification component for supplying the converted component to the ozone generator through a supply pipe;
It is characterized by having.

  According to the method for producing ozone ice of the present invention, a system capable of producing ozone ice easily and inexpensively can be constructed, food transportation and storage efficiency (including cost) can be dramatically improved, and the food distribution system can be greatly improved. Can make a contribution. For example, a so-called “modal shift” from a truck to a railway can be achieved because the storage / transportable period becomes longer. In addition, foods that can be converted from frozen to refrigerated can be increased. In addition, if ozone ice is used instead of sodium hypochlorite for sterilization and washing at food factories and food retailers, the environmental impact of wastewater can be significantly reduced. As described above, this is because the production method using the ozone ice and the production apparatus of the present invention can sufficiently contribute to the environment from the viewpoints of reduction of transportation / storage energy and replacement with the conventional disinfectant.

  Hereinafter, the manufacturing method of ozone ice will be described for each stage (process) with reference to FIG.

(1) Ozone Generation Stage First, the ozone ice manufacturing method of the present invention includes an ozone generation stage in which ozone is generated by the ozone generator 15 from the raw material supplied from the ozone raw material section 11 through the pipe 13.

Here, in the case of a discharge type (using oxygen) as the ozone generator 15, the amount of oxygen supplied from the ozone raw material part 11 through the pipe 13 is the size of the water tank 33 to be used and the size of the cooling surface of the cooling member 27. Since it varies depending on the situation, it cannot be defined uniquely. However, in general, the water tank 33 used in the embodiment has a volume of 20 L of microbubbles stored in 30 L (liters), a supply flow rate of 5 L / min of microbubbles mixed water into the water tank 33, and the cooling surface 27 a of the cooling member 27. When the area is 64 cm ^2, the amount of oxygen supplied from the ozone raw material part 11 is 0.44 to 0.46 L / min.

  As the ozone concentration (the amount of ozone generated) in the ozone-containing gas (= ozone + oxygen) generated by the ozone generator 15 in the ozone generation stage (1), the type (method) and performance of the ozone generator 15 Although it varies depending on the use conditions, purpose of use, use, etc., the higher the value, the better the sterilizing / deodorizing effect, which is preferable. Specifically, in the case of a discharge type (using oxygen) as the ozone generator 15, it is 2.5 vol% or more, preferably 2.5 to 7.5 vol%, preferably 5.0 vol% with respect to the supplied oxygen. % Or more, more preferably about 7.5% by volume. If it is less than 2.5% by volume with respect to the supplied oxygen, the ozone concentration of the generated ozone ice may not reach the ozone concentration necessary for sterilization and deodorization. Even if the ozone concentration (amount of ozone generated) exceeds 7.5% by volume, it can be used without any problems, but the expensive and used models of ozone generators that can be continuously produced are greatly limited. In addition, since the apparatus tends to increase in size, the manufacturing cost and running cost may increase. Even when the ozone generator 15 of a system other than the discharge type (using oxygen) is used, the ozone concentration (amount of ozone generated) in the ozone-containing gas generated by the ozone generator 15 is the above discharge type. It is desirable that the ozone concentration (amount of ozone generated) in (using oxygen) be the same. In the following various experiments, the ozone concentration in the ozone-containing gas generated by the ozone generator 15 was performed using an apparatus having 7.5% by volume (product catalog value) with respect to the supplied oxygen. The ozone concentration in the ozone-containing gas (= ozone + oxygen) relative to the supplied oxygen can be measured using the KI method (potassium iodide (KI) method defined in JIS B7957) or the like.

  However, in this ozone generation stage, the component (ozone + oxygen) gasified by the microbubbles in the water mixed with microbubbles may be supplied (reused) from the water tank 33 to the ozone generator 15 through the pipe 39. In this case, ozone gas having a concentration higher than the ozone concentration described above can be generated.

(2) Bubble mixed water generation stage Next, in the ozone ice manufacturing method of the present invention, the ozone-containing gas (= ozone + oxygen) generated by the ozone generator 15 in the ozone generation stage and the pipe 19 from the water tank 33 are shown. Water that is supplied (circulated) and / or water that is supplied from the outside through the pipe 21 is introduced into the microbubble mixing device 23 to generate a bubble mixed water generation stage for generating microbubble mixed water.

  The amount of water supplied to the ozone-containing gas introduced into the microbubble mixing device 23 is within a range that does not impair the effects of the present invention (a range in which ozone ice having a desired high bubble content can be created. )), There is no particular limitation. If the amount of water supplied to the ozone-containing gas is within the above range, the dissolved ozone concentration of the obtained microbubble-containing water can be made a saturated concentration, and the microbubble-containing water in the microbubble 29 The ozone (gas) concentration (average value) can be controlled within a suitable range shown below. If the amount of water supplied to the ozone-containing gas is within the above range, the ozone-containing gas is highly dispersed as micro-sized bubbles (bubbles) without excessive ozone-containing gas. It is also excellent in that it can be easily mixed. Furthermore, if the amount of water supplied to the ozone-containing gas is within the above range, the small microbubble mixing device 23 can be used, and the entire device 10 can be downsized, and transport of fresh foods is possible. It can be installed in trucks, freight trains, domestic and overseas air freight flights, domestic and overseas cargo ships, which are institutional cold storage functions, and always supply a certain amount of ozone ice to fresh food during transportation. It is excellent in that it can be done.

  The solubility of ozone in water in the microbubble mixing device 23 varies depending on the device configuration and conditions, but in consideration of the device configuration of the present embodiment, the microbubble mixed water obtained by the device 10 of the present embodiment. The dissolved ozone concentration (the solubility of ozone in water) (average value) can be said to be a saturated concentration. That is, compared with the case where a bulk ozone-containing gas is added to water and dissolved, in the present invention, since the microbubble-like ozone-containing gas is added to water and dissolved, the contact area between the water and the microbubble surface is reduced. It can be said that it is remarkably large and can be quickly dissolved to a saturated concentration.

  Moreover, the content rate (volume%) of the microbubble 29 in microbubble mixing water (in other words content of the microbubble 29 in the ozone water 31 of the water tank 33) (average value) is 8-11 volume%. If the content (volume%) of the microbubbles 29 in the microbubble mixed water is 8% by volume or more, the high bubble content of the present invention can be obtained by combining with the shape and arrangement of the cooling surface 27a of the cooling member 27 described above. It is possible to make ozone ice having On the other hand, if the content (volume%) of the microbubbles 29 in the microbubble-mixed water is 11% by volume or less, the ozone-containing gas becomes excessive, and the microbubbles 29 are bonded to each other while being transported in the pipe 25, and the bubble size Ozone ice having a high bubble content according to the present invention can be controlled by dispersing a micro size of a desired size in micro bubble-mixed water and transporting and injecting it into the water tank. It is excellent in that it is easy to make ice. The method for measuring the content (volume%) of microbubbles in the water mixed with microbubbles can be measured using a method for measuring the volume increase due to the inclusion of bubbles.

  Furthermore, the total of the dissolved ozone concentration in the microbubble-containing water and the ozone (gas) concentration in the microbubble 29 is 1 ppm or more, preferably 1 to 5 ppm, more preferably 5 ppm. However, it goes without saying that the concentration may be as high as 30 ppm or more. If the total concentration of ozone (gas) in the microbubble 29 with the dissolved ozone concentration in the microbubble mixed water is 1 to 5 ppm, the ozone ice having a high bubble content according to the present invention obtained by ice making has high sterilization as well as cooling properties. -It is possible to contribute effectively, which is very effective in maintaining the deodorizing action for a long time. On the other hand, the upper limit value of the ozone (gas) concentration in the microbubbles 29 in the water mixed with microbubbles is not particularly limited. The higher the ozone concentration, the higher the ozone ice content of the present invention obtained by ice making. It is extremely effective and effective in maintaining a high sterilization and deodorizing action for a long period of time as well as a cold insulation property. However, the ozone generation amount (performance) of the discharge-type ozone generator 15 is limited due to the above-described apparatus configuration. When such an ozone generator 15 is used, the dissolved ozone concentration and the microbubbles in the microbubble mixed water are reduced. The total ozone (gas) concentration in the bubble 29 is approximately 30 ppm or more in the current apparatus. However, the amount of generated ozone can be increased by using a large number of ozone generators 15 such as a discharge type in combination or increasing the size. However, the size of the apparatus is increased, and the equipment cost and running cost (production cost) may be increased. Therefore, it can be said that it is desirable to select the ozone generator 15 having the optimum scale according to the purpose of use.

  Moreover, the distribution of the microbubble diameter in the water mixed with microbubbles that can be used in the production method of the present invention is in the range of 10 μm to 100 μm when a pressure dissolution type device (example of FIG. 1A) is used as the microbubble mixing device 23. It is. As a method of measuring the microbubble diameter and its average value, a laser diffraction scattering method or the like can be used.

That is, the microbubble diameter in the microbubble mixed water produced by the microbubble mixing apparatus 23 that can be used in the production method of the present invention is 10 to 100 μm, preferably 10 to 50 μm, more preferably 10 to 30 μm.
When the microbubble diameter becomes larger than the range of 100 μm, the size of bubbles taken into ozone ice during ice making becomes too large, and large air bubbles can be blown when performing cold storage, sterilization, and deodorization. Will be released to the atmosphere. Therefore, there is a possibility that long-term cold preservation and sterilization / deodorization action due to the release effect when the microbubbles gradually flip can be difficult to obtain. On the other hand, it is difficult in terms of device performance to make the microbubble diameter smaller than 10 μm. However, within the range that does not impair the effects of the present invention, even if the microbubble diameter in the microbubble mixed water and the average value thereof are out of the above range, they can be included in the technical scope of the present invention. .

  Even in the manufacturing method of the present invention, the ozone water supplied from the water tank 33 through the pipe 19 and / or the water supplied from the outside through the pipe 21 is used when the apparatus is continuously operated. This is because it is necessary to supply water from the outside through the pipe 21 in accordance with the amount of water taken out. On the other hand, during the ice making of the ozone ice 39, since the ice making device (for example, the refrigerant circulation device 37) is operated from the state where the water tank 33 is filled with a necessary amount of water, it is not necessary to replenish water from the outside. It is desirable that ozone water is supplied from the water tank 33 through the pipe 19 and circulated. This is because the ozone half-life is sufficient in water as described above, and when the production time of one ozone ice is 40 minutes (see Examples), the ozone water 31 in the water tank 33 is used without such circulation. When the ozone ice 39 is produced, the ozone in the ozone water 39 is gradually decomposed and the ozone concentration of the ozone water 31 is lowered. Therefore, the ozone water 31 in the water tank 33 is circulated to generate new microbubble mixed water. This is because it is desirable to supply. On the other hand, regarding the ozone-containing microbubbles 29, the ozone half-life of the ozone in the gas is as long as several hours to several tens of hours, and the ozone-containing microbubbles supplemented to the cooling surface (ice-making surface, heat transfer surface) 27a of the cooling member 27. There is no need to extract 29. Therefore, as shown in FIG. 1 and FIG. 2A2 to FIG. 2G2, ozone water 31 in which the ozone-containing microbubbles 29 are not mixed from the lower part of the water tank 33 on the side opposite to the supply side of the microbubble-mixed water (the farthest position). In order to be extracted and regenerated, it is preferably supplied to the microbubble mixing device 23, regenerated to saturated ozone water (microbubble mixed water), and returned to the water tank 33. In addition, since the half-life of ozone dissolved in the ozone ice 39 is longer than the half-life of ozone in the ozone water 31, it can be stored in the ozone ice 39 to exhibit a long-term cooling and sterilizing / deodorizing effect. I can say what I can do.

(2a) Chlorine removal step Further, in the production method of the present invention, in the bubble mixed water generation stage (2), on the path of the pipe 19 for supplying water supplied from the water tank 33 to the ozone generator 15 and / or outside It is desirable to have a step (chlorine removing step) of removing chlorine (chlorine-containing component) in the water using a chlorine removing device 49 installed on the path of the pipe 21 for supplying water supplied from.

The chlorine removing step is particularly effective when the ozone ice 39 is made using tap water containing chlorine. When using tap water, the cost reduction effect is large and advantageous as compared with the case where distilled water is used. Furthermore, it is because the removal of chlorine from tap water provides an effect of increasing dissolved ozone and the amount of ozone in the bubble-containing microbubbles 29, and further the amount of microvalves themselves (see FIG. 13). Normally, tap water contains a lot of residual chlorine, trihalomethane, and the like. This residual chlorine is a residue of chlorine used for sterilization at the water purification plant and chlorine for preventing bacteria from breeding before the tap water enters the household water supply pipe. This residual chlorine keeps tap water safe and at the same time is a very dangerous substance for the body. Therefore, the water in the faucet (= the side of the entrance, where there is a water meter. The entrance of the water supply to each house) is free residual chlorine (= hypochlorite ion remaining in the tap water (= ClO ⁻ )) at 0.1 mg / liter (bound residual chlorine (= 0.4 mg / liter in the case of chloramines (NHCl ₂ , NH ₂ Cl, etc.) remaining in tap water)) It is supposed to be disinfected. However, free residual chlorine in water in the hydrant when the supplied water may be significantly contaminated by pathogenic organisms or when there is a risk of containing a large amount of organisms or substances that are suspected of being contaminated by pathogenic organisms Is 0.2 mg / liter or more (1.5 mg / liter in the case of combined residual chlorine). From the above, chlorine contained in tap water includes trihalomethane, etc. in addition to residual chlorine, free residual chlorine, combined residual chlorine, and the like. This is because trihalomethane is a carcinogenic substance generated when chlorine sterilization is performed at a water purification plant, and is a chlorine-derived substance. If the water source is polluted, adding more chlorine increases the possibility that more trihalomethane will be generated, and trihalomethane can react with ozone in the same way as chlorine to detoxify (ozone disinfection). However, since the ozone concentration in the water mixed with microbubbles is reduced by that amount, it is desirable to remove them before the microbubble mixing device 23.

  Therefore, in the chlorine removing process of the present invention, from the beginning of the operation of the apparatus 10 until the required amount of ozone water 31 is filled in the water tank 33, the microbubble mixing apparatus 23 is passed through the piping 21 path for supplying tap water from the outside. A necessary amount of water (ozone water) 31 is supplied to the water tank 33. Therefore, by installing the chlorine removing device 49 on the path of the pipe 21, chlorine can be effectively removed, and decomposition of ozone can be extremely effectively prevented by the chlorine.

  On the other hand, after the required amount of water (ozone water) is supplied to the water tank 33, the supply of tap water from the pipe 21 path is stopped, and the microbubble mixing device 23 is supplied through the pipe 19 path for supplying ozone water from the water tank 33. The ozone water 31 is supplied to the water, and the microbubble mixed water obtained by the mixing device 23 is supplied to the water tank 33 and circulated. At this time, only when chlorine in tap water supplied through the pipe 21 route is not completely removed by the chlorine removing device 49 on the pipe 21 route, the chlorine removing device (see FIG. (Not shown) can effectively function to decompose chlorine slightly remaining in the ozone water 31.

(3) Bubble mixed water supply stage Next, in the manufacturing method of the present invention, the microbubble mixed water generated in the bubble mixed water generation stage (2) is continuously or intermittently cooled on the cooling surface of the cooling member 27. The bubble mixed water supply stage in which the tip end 25a of the bubble mixed water supply pipe 25 and the cooling member 27 are supplied to the water tank 33 disposed inside the tank so that the microbubbles 29 can be captured under 27a. Have

(A) Microbubble mixed water injection method When microbubble mixed water is continuously injected (supplied) into the water tank 33, the amount of ozone microbubbles contained is increased as compared to intermittent supply. In addition, the amount of incorporation into the obtained ozone ice 39 is increased, and as a result, the ozone ice 39 having a high bubble content can be formed. On the other hand, when microbubble-mixed water is intermittently injected (supplied) into the water tank 33, the microbubble-mixed water stop time and stop timing are adjusted as compared with the case of continuous supply. The contained bubble (bubble) diameter in the ozone ice 39 having a high bubble content can be controlled. As a result, it is possible to provide the ozone ice 39 that can provide the ozone gas release effect according to the intended use.

(B) Arrangement of the tip 25a of the supply pipe 25 and the inside of the water tank 33 of the cooling member 27 The tip 25a of the supply pipe 25 of bubble mixed water and the cooling member 27 are arranged inside the water tank 33, 1, 2A2, 2A3, 2B2, 2C2, 2D2, 2E2, 2F2, and 2G2, a large number (substantially in the water tank) is formed below the cooling surface 27a of the cooling member 27 during ice making. Ozone ice 39 grows under the cooling surface 27a by intensively collecting a group of microbubbles 29 (total amount / substantially all number) in a concentrated manner (in a lumped state, aggregated state, accumulated state or agglomerated state). In the process of (generation), it is possible to maintain a state in which a large number of microbubbles 29 are always present (aggregated) on the ice making surface. Therefore, a large number of microbubbles 29 are efficiently taken into the ozone ice 39, and some A large number of bubbles having a size in which the microbubbles 29 are combined can be contained.

(B1) Disposition of the distal end portion 25a of the supply piping 25 Therefore, the distal end portion 25a of the piping 25 is shown in FIGS. 1, 2A2, 2A3, 2B2, 2C2, 2D2, 2E2, 2F2, and 2G2. As shown in the figure, the lower part of the water tank 33, the flat cooling member 27 has a cooling surface (ice-making surface) 27 a below (lower side), and the cylindrical cooling member 27 has a cooling surface (ice-making). It is desirable that the surface is penetrated (communicated) to a position where the microbubbles 29 can be easily captured effectively (extended) inside (inside) 27a. With this configuration, the micro-bubbles are floated (floating) along the flow of the microbubble-mixed water supplied from the tip of the pipe 25, and the micro-structure is formed below (or inside) the ice making surface (cooling surface) 27 a below the cooling member 27. This is because the bubbles 29 can be captured effectively (= a large amount) (see FIGS. 1 and 2). Therefore, the distal end portion 25a of the pipe 25 can be appropriately adjusted so as to be in an optimum position according to the flow rate (flow rate) of the microbubble mixed water, the size of the water tank 33, the structure and arrangement of the cooling member 27, and the like. In addition, it is desirable to have a structure that can expand and contract in the front-rear direction and bend and extend in the vertical and horizontal directions.

(B2) Arrangement of cooling member 27 As shown in FIGS. 1, 2A2, 2A3, 2B2, 2C2, 2D2, 2E2, 2F2, and 2G2, the arrangement of the cooling member 27 is as follows. What is necessary is just to arrange | position so that a cooling surface may be under the liquid level in the water tank 33. FIG.

(B3) Cooling surface angle of the flat cooling member 27 (heat transfer surface posture)
From FIG. 1 to FIG. 11 (particularly FIG. 3), the cooling surface angle (heat transfer surface posture) of the flat cooling member 27 of the present invention is preferably 0 ° (horizontal) to 60 °, preferably 0 ° to It is in the range of 45 °, more preferably 10 to 45 °, particularly preferably 10 to 15 °. FIG. 3A shows that the bubble content (volume%) decreases as the cooling surface angle increases. When the cooling surface angle is 0 °, the bubble content is about 28% by volume, whereas when the cooling surface angle is 90 °, the bubble content is about 7% by volume.

  However, looking at the photograph (drawing) of ice with a cooling surface angle of 0 ° in FIG. 4, there is a large hole on the surface, and the measurement result of the bubble content (volume%) has increased due to the influence of the hole. Seem. However, when the cooling surface angle is gradually inclined, as shown in FIGS. 5 to 8, large holes on the surface tend to gradually decrease.

  When the tendency is observed in detail, when the cooling surface angle is 10 to 15 °, the bubble content rate is greatly increased as compared with the case where the cooling surface angle is 20 ° (see FIG. 3). When the cooling surface angle is 20 to 45 °, the bubble content is hardly changed. When the cooling surface angle is 90 °, the bubble content is reduced to about half compared to the case where the cooling surface angle is 20 to 45 °. . The white spots in ice are contained bubbles. Therefore, from FIG. 3, it can be said that the cooling surface angle is optimally 10 to 15 ° in consideration of the bubble content. The bubble content at that angle is about 22% by volume. This value is about four times as large as 6% by volume reported so far (see Patent Document 1).

  The cooling surface angle is an example in which the cooling member 27 has a flat plate shape, and in the case of other polygonal shapes such as a triangle, pentagon, and hexagon, a disc shape, a corrugated plate shape, etc., FIGS. The optimum cooling surface angle may be determined as appropriate by conducting a preliminary experiment in accordance with the experiment shown in FIG.

(C) Injection amount of microbubble mixed water The injection amount of microbubble mixed water includes the size of the water tank 33, the shape of the cooling member 27, the size and shape of the cooling surface (ice making surface) 27a, the ice making temperature, the ice making speed, and the like. Therefore, the supply amount of the necessary microbubbles 29 to be injected into the water tank 33 is determined by the water mixed with microbubbles. That is, the amount of microbubbles 29 taken into the ozone ice 39 per unit time is determined by the ice making speed on the lower side (or inside) of the cooling surface (ice making surface) 27a of the rejection member 27 provided in the water tank 33. Therefore, it is sufficient to supply (replenish) an amount of microbubbles 29 that can compensate for this, and the supply amount of microbubbles 29 is determined. Therefore, the injection amount of the microbubble mixed water necessary for replenishing the supply amount of the microbubbles 29 may be appropriately determined. That is, since the amount of the microbubbles 29 in the water mixed with microbubbles can be arbitrarily adjusted, if the supply amount of the necessary microbubbles 29 is determined, an appropriate injection amount of the microbubble mixed water can be determined. . As a rough guide, the flow rate of the water mixed with microbubbles into the water tank 33 is 5 L / min. This is the supply flow rate when the ozone water 31 is supplied to the microbubble mixing device 23 through the pipe 19, and the microbubble mixing water that further reaches the supply (circulation) from the microbubble mixing device 23 to the water tank 33 through the pipe 25. It can be said that the circulation speed (supply flow rate). If the flow rate of the water mixed with microbubbles into the water tank 33 is about 5 L / min, the cooling surface (ice making surface) 27a of the rejection member 27 of the microbubbles 29 in the water mixed with microbubbles into the water tank 33 (or the inner side) Ozone ice having a high bubble content can be produced. If the flow rate of the water mixed with microbubbles into the water tank 33 is about 5 L / min, the microbubbles 29 in the water mixed with microbubbles into the water tank 33 will be excessive, and will float and gasify on the liquid level without being completely captured. The amount of microbubbles that are generated can be suppressed, and ozone ice having a high bubble content can be produced.

(D) Amount of microbubbles 29 in the water mixed with microbubbles The amount of microbubbles 29 in the water mixed with microbubbles is not particularly limited, but is 8 to 11% by volume in the current apparatus. However, it is not limited to the above range in the current apparatus, and is within the technical scope of the present invention as long as it is within the range where the effects of the present invention can be achieved even outside the above range. Needless to say. When the amount of microbubbles 29 in the microbubble mixed water is less than 8% by volume in the current apparatus, the injection speed of microbubble mixed water (= supply from the pipe 25 to the water tank 33 through the microbubble mixing apparatus 23 from the pipe 19) The total circulation speed up to the above) must be increased to supplement the necessary supply amount of the microbubbles 29, and a powerful circulation device (pump) is required, and the load on the microbubble mixing device 23 is increased. There is a risk that it will lead to cost increase such as early maintenance and replacement time. If the amount of microbubbles 29 in the microbubble-mixed water exceeds 11% by volume with the current apparatus, the amount of microbubbles 29 in the microbubble-mixed water is greatly increased in density, and the injection speed of microbubble-mixed water (= pipe) 19), the circulation speed from the pipe 25 through the microbubble mixing device 23 to the supply to the water tank 33 is slowed down. There is a risk of increasing. In addition, a powerful circulating device (pump) is required for transferring gas-liquid mixed water including a large amount of microvalves 29. A method for measuring the amount of microbubbles 29 in the water mixed with microbubbles can be measured by measuring the volume increase due to the inclusion of bubbles.

(4) Ozone Ice Generation Stage Next, in the production method of the present invention, the microbubbles 29 are trapped on the lower side (or inside) of the cooling surface 27 of the cooling member 27 by the bubble mixed water supply stage (3). Then, the refrigerant is circulated from the refrigerant circulation device 37 to the circulation flow path 35 inside the cooling member 27 to cool at least the cooling surface 27a of the cooling member 27, and the bubbles 29a are formed below (or inside) the cooling surface 27. An ozone ice generating step for generating ozone ice 39 containing the above.

(A) Refrigerant used for cooling the cooling surface 27a Here, as the refrigerant (brine; including antifreeze liquid), as long as the cooling surface 27a of the following cooling member 27 can be cooled to the cooling temperature range shown below, It is not limited, and the same ones as described in the manufacturing apparatus can be used. Specific examples include brines such as ethylene glycol and ethanol, ammonia, carbon dioxide gas, sulfurous acid gas, alternative refrigerants, and the like, but are not limited thereto. In the chloride solution (brine), the freezing temperature can be adjusted by adjusting the concentration thereof, and the cooling surface 27a of the cooling member 27 can be cooled to the cooling temperature range shown below.

(B) Refrigerant temperature The refrigerant temperature is in the range of -20 to -22 ° C. When the temperature of the refrigerant is higher than −20 ° C., even if the copper cooling member 27 having good thermal conductivity is used, it takes a long time to make ice to a predetermined thickness, and the production cost is low. In addition to an increase in the cooling surface temperature, the cooling rate decreases due to an increase in the temperature of the cooling surface. On the other hand, the lower limit of the temperature of the refrigerant is not particularly limited. However, when the temperature is lower than −22 ° C., the usable refrigerant is limited, an expensive refrigerant is required, and the running cost is increased. There are also problems such as a decrease in heat transfer coefficient due to a decrease in the viscosity of the refrigerant.

(C) Temperature of the cooling surface 27a of the cooling member 27 The temperature of the cooling surface 27a of the cooling member 27 using the refrigerant is in the range of −6.8 to −13 ° C., more preferably −10 to −13 ° C. When the temperature of the cooling surface 27a is higher than −6.8 ° C., it takes a long time to make ice to a predetermined thickness, which increases the production cost and reduces the amount of bubbles taken in as the ice making speed decreases. Undesirable, for example, a reduction occurs. On the other hand, the lower limit value of the temperature of the cooling surface 27a is not particularly limited. The lower the temperature of the cooling surface 27a, however, when the temperature is lower than −13 ° C., the types of refrigerants that can be used and the types of cooling members are limited, and expensive refrigerants are required, and the running cost increases.

(4a) Exhaust process / reuse process In the production method of the present invention, during the ozone ice generation stage (4), the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 float on the liquid surface and become a gas. The exhausting process for exhausting the gasified component from the water tank 33 to the outside of the system through the exhaust pipe 41 and / or the gasified component in which the microbubbles 9 in the microbubble mixed water are floated on the liquid surface The recycling process of the gasified component supplied to the ozone generator 15 through the pipe 19 is performed.

(A) Exhaust process In the exhaust process, the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 are floated on the liquid surface and gasified components are exhausted from the water tank 33 to the outside through the exhaust pipe 41. This prevents the internal pressure of the sealed water tank 33 from increasing and leaking liquid from the water tank 33 and joints of various pipes. By carrying out such an exhausting process, it is not necessary to make ice under high pressure (pressurized) conditions, and it is excellent in that a small and inexpensive device can be used without using a pressure-resistant water tank (container) or piping. Yes. Accordingly, in the exhaust process of the present invention, the exhaust pipe 41 is not provided, and the upper part of the water tank 33 without the upper lid 33a is made an open system (opening) instead of the sealed water tank 33, so that the natural exhaust is performed. Also good.

  However, since ozone gas is contained, it is desirable to exhaust to a safe area away from the work site by using an exhaust pipe because the work environment deteriorates.

(B) Reuse process In the reuse process, the components generated by the gas bubbles generated by the microbubbles 9 in the microbubble-mixed water supplied into the water tank 33 are piped from the water tank 33 to the ozone generator 15. By supplying through 19, the gasified component can be reused (regenerated).

  Furthermore, also in this reuse process, the internal pressure of the sealed water tank 33 is increased, and liquid leakage from the water tank 33 and joints of various pipes is prevented. By carrying out such a reuse process, it is not necessary to make ice under high pressure (pressurized) conditions, and it is not necessary to use a pressure-resistant water tank (vessel) or piping, which is excellent in that a small and inexpensive device can be used. ing.

(4b) Moisture removal step In the production method of the present invention, when the recycling step (4a) is carried out during the ozone ice generation step (4), the ozone generator 15 contains microbubble-containing water. Water removal from the gasified component is performed using a moisture removing device 45 installed in the pipe 43 path for supplying the gasified component (ozone + oxygen) floating on the liquid level of the water tank 33. It is desirable to use a process to be performed (moisture removal process) in combination.

  This is a case where water vapor (moisture) is contained in the component (ozone + oxygen) gasified by floating the microbubbles 29 in the water mixed with microbubbles above the liquid surface (wet gas). In such a case, the moisture generator 45 (especially in the case of a discharge ozone generator) is provided with a moisture removal means 45 in the path of the pipe 43 for supplying the gasified wet gas component, so that such moisture can be effectively obtained. Can be removed as a dry gas component. The ozone concentration can be raised with respect to the gasified component (dry gas component) supplied to the ozone generator 15 by the reuse after removing the moisture in the gasified component. As a result, it is excellent in that the dissolved ozone concentration in the microbubble mixed water obtained from the ozone generator 15 through the microbubble mixing device 23, the ozone concentration in the microbubble, and the microbubble amount itself can be increased.

(A) Moisture removing means 45
The moisture removing means 45 is not particularly limited, and conventionally known moisture removing means can be appropriately used as described in the production apparatus [II] of the present invention. This is because ozone containing humidity (moisture) is very corrosive, and therefore it is desirable to remove the moisture, preferably immediately after removal from the water tank, before returning to the ozone generator 15 to prevent corrosion. . Preferably, as the moisture removing means 45, (a) a part 43a of the pipe 43 for supplying the gasified component to the ozone generator 15 is provided with a detachable and enlarged diameter portion 43a, and the enlarged diameter position 43 is provided. Further, it is desirable that a Peltier element 45a for cooling and dehumidifying (and removing moisture) the gasified component is disposed. Alternatively, (b) the supply pipe 43 is preferably filled with a moisture absorbent 45b such as silica gel for adsorbing and removing moisture from the gasified component. Further, as a configuration combining (a) and (b), (c) a Peltier element 45a is disposed in the enlarged diameter portion 43, and a hygroscopic agent 45b such as silica gel is disposed in the front and / or rear pipe 43. May be filled. However, the present invention is not limited to these. In addition, the moisture removing means 45 is not limited in the case of being arranged at one place, and may be installed at a plurality of places. In particular, it is desirable to appropriately arrange the Peltier elements 45a that do not require periodic replacement. When the moisture absorbent 45b such as silica gel is filled, the moisture absorption (moisture removal) ability gradually decreases due to moisture adsorption, so the moisture content in the gasified component (dry gas component) supplied to the ozone generator 15 As the Peltier element needs to be replaced regularly, the load on the ozone generator 15 may be generated, and the manufacturing cost may be slightly increased.

(B) Moisture removal rate By the water removal process from the wet gas in which water vapor (water) is contained in the component (ozone + oxygen) in which the microbubbles 29 in the microbubble mixed water float and gasify on the liquid surface The moisture removal rate is 95 to 99%, more preferably 98 to 99%. In other words, the moisture content in the dry gas after moisture removal by the moisture removal step is 5% or less, more preferably 1% or less. The higher the moisture content, the more easily the piping of the ozone generator 15 is corroded. By setting the moisture content in the dry gas after moisture removal in the moisture removal step to 5% or less, the ozone concentration can be increased with respect to the gasified component (dry gas component) supplied to the ozone generator 15. . As a result, it is excellent in that the dissolved ozone concentration in the microbubble mixed water obtained from the ozone generator 15 through the microbubble mixing device 23, the ozone concentration in the microbubble, and the microbubble amount itself can be increased.

(4c) Voltage application process In the manufacturing method of this invention, it is desirable to implement the voltage application process which applies a voltage to the said cooling member 27 using the power supply device 47 in the said ozone ice production | generation stage (4). This is because the amount of microbubbles 29 on the cooling surface 27a of the cooling member 27 can be increased by 50% or more depending on conditions such as the magnitude of voltage application (see FIG. 12).

(A) Applied voltage The voltage (preferably DC voltage) applied to the cooling member 27 is not particularly limited, and a voltage value similar to that described in the manufacturing apparatus can be used. Specifically, it may be a voltage value exceeding 0 V, but is preferably 50 V or more, preferably 100 V or more, more preferably 100 to 300 V, and particularly preferably 200 to 300 V. Depending on conditions such as the magnitude of the applied voltage, the amount of microbubbles on the cooling surface 27a of the cooling member 27 can be increased to about 30% by volume (see FIG. 12A). In addition, the average value of the ratio (volume%) of bubbles on the wall surface (cooling surface 27a) on the vertical axis in FIG. A value (average value of 10 samples) calculated by performing image analysis processing on bubbles as a sphere when viewed in an image is used.

  Further, when the flat cooling member 27 is installed horizontally, the bubble content of ice with respect to the bubble concentration in water can be increased to about 110 to 150% depending on conditions such as the magnitude of the applied voltage. On the other hand, in the example of Patent Document 1 in which the flat cooling member 27 is installed vertically, the bubble content of ice with respect to the bubble concentration in water is 30 to 60% by volume (ozone ice) depending on conditions such as the magnitude of the applied voltage. The gas content is about 6% by volume), and the effect of voltage application to the cooling member 27 cannot be enjoyed at all (see FIG. 12B).

The applied voltage may be a constant voltage value during ice making, or can be varied during ice making as long as it is within the above range. Further, the applied voltage may be applied continuously during ice making, or may be applied intermittently (intermittently).
[IIIa] Method for Producing Ozone Ice Slurry of First Embodiment The method for producing ozone ice slurry according to the first embodiment of the present invention is the same as the method for producing ozone ice of the present invention described in [III] above, and further the ozone ice slurry. The flow rate of water supplied to the mixing device 23 through a supply path (= pipe 55) provided with a flow rate adjusting device (for example, a flow rate adjusting valve) 53 from the additive storage unit 51 to the microbubble mixing device 23 It has the step which supplies the said additive by a predetermined ratio (volume ratio) with respect to.

  In the manufacturing method of the ozone ice slurry of the first embodiment, by making the ozone ice 39 into an aqueous solution, the liquid temperature can be lowered and the ozone solubility can be increased. Moreover, the ozone ice slurry (39a) has fluidity and good thermal load followability. Therefore, the ozone ice slurry (39a) can be filled (supplied) along the shape of fresh fish or the like without any gaps, and the cold-retaining property and the sterilizing / deodorizing effect can be significantly improved. In addition, the ozone ice slurry (39a) can be provided in a temperature range suitable for the optimum storage or transportation temperature of the produced food, and the freshness retention effect of the produced food is remarkably enhanced and stable for a long time. And freshness can be maintained. Further, if necessary, when the fresh food is stored in a quick freeze (−18 ° C. or lower) and kept fresh, the heat load followability is good. For example, propylene glycol (PG) is used as the additive. In this case, an ozone ice slurry (39a) that can be refrigerated in a temperature range of −18 ° C. or lower can be provided by setting the initial concentration of PG to 25% by volume or more.

(1) Additive of ozone ice slurry The additive is not particularly limited as long as it can be made into an ozone ice slurry. For example, propylene glycol (PG) or ethanol or salt water of a predetermined concentration (preferably In the ozone ice slurry 39a, the salinity concentration is adjusted to be the salinity concentration in the seawater). However, it is not limited to these. The additives exemplified above, PG or ethanol, or salt water of a predetermined concentration are all food additives, and even when they are taken into the ozone ice slurry 39a, they are kept cold during storage or transportation of fresh foods or the like. Can be used without problems. Two or more of the above additives may be used in appropriate combination.

(A) Additive concentration of ozone ice slurry Additive concentration of ozone ice slurry, that is, an additive concentration (ratio; volume ratio) to the flow rate of water supplied to the mixing device 23 is 5 to 25% by volume. Preferably it is 15-25 volume%, More preferably, it is the range of 20-25 volume%. This is because, if the additive concentration is 25% by volume, the food can be refrigerated in a wide temperature range up to about -15 to -18 ° C necessary for normal food refrigeration. In addition, when refrigerated to about -18 ° C, such foods can be cooled to such a low temperature that water and fats and oils can freeze and solidify, suppressing the activity of microorganisms, and for a long time (according to the Japan Frozen Food Association, -18 ° C). If it is below, it can be preserved for about one year after production), which is excellent in that long-term transportation and preservation can be realized.

  In addition, since the aqueous solution of ozone in which the additive is dissolved, the solute (additive) is discharged from the ice part into the aqueous solution along with freezing, so the concentration of the liquid (unfrozen part) in the generated ice slurry is the initial value of the additive. It becomes higher than the concentration.

  Further, the refrigeration temperature (ozone ice slurry temperature) can be controlled by adjusting the initial concentration of the additive. For example, by adjusting the initial concentration to 5% by volume in PG, it is possible to produce an ozone ice slurry 39a that can be refrigerated in a temperature range of about −4 ° C. As the PG concentration is increased, refrigeration at a lower temperature is possible. A possible ozone ice slurry 39a can be produced. For example, by adjusting the initial concentration of PG to 25% by volume, it is possible to produce an ozone ice slurry that can be refrigerated (refrigerated) in a temperature range of about −18 ° C. that can be frozen.

  In addition, the ozone ice slurry using salt water of a predetermined concentration is particularly suitable for maintaining the freshness of marine fish and shellfish by adjusting the concentration of seawater when the ice slurry is turned into an aqueous solution. In addition, ozone ice slurry using salt water is superior in that it has a low temperature holding performance superior to that of fresh water ice. Furthermore, by using an ozone ice slurry, the fluidity increases as described above, and high-density heat transport becomes possible. Moreover, since the contact area with respect to one fish becomes large, a fish can be cooled uniformly and rapidly. Thus, it can be said that the ozone ice slurry using salt water is suitable for maintaining the freshness of fish. In particular, deep ocean water is superior in that it has less spoilage bacteria than surface water and can produce ozone ice slurry using salt water that is hygienic. Moreover, the temperature of deep ocean water is 8-10 ° C throughout the year, and the surface water is 16-25 ° C. The temperature difference is large, and it is also excellent in that ice can be made with a small amount of electric power when ice is produced. .

As described above, the initial concentration of the additive is difficult to define uniquely, and within the range that does not impair the effects of the present invention, the characteristics of each additive described above are used for each application. What is necessary is just to adjust suitably and use for an optimal density | concentration. It can be said that the optimum concentration for each application is desirably obtained in advance by conducting a preliminary experiment or the like.
[IIIb] Method for Producing Ozone Ice Slurry of Second Embodiment The method for producing ozone ice slurry of the first embodiment of the present invention is the same as the method for producing ozone ice of the present invention described above in [III], and further includes a cooling member. Ozone ice generated on the cooling surface is scraped with an ice scraping method by (a) scraping the ice peeled by the harvest method using an ice scraping device and making it into a slurry, or scraping using an ice scraping device. And taking a slurry. Both methods can be easily generated and contain additives in that ozone ice slurry can be generated by scraping or scraping the generated ozone ice (including dissolved ozone and ozone bubbles). Therefore, the cost required for the additive is unnecessary, and since it becomes water after dissolution, it is excellent in that post-treatment (cleaning, recovery, etc.) is unnecessary.
[V] Taste and fragrant ice confectionery having a high ice gas content (volume ratio) The taste and fragrance ice confectionery of the present invention is obtained by using the production apparatus of the present invention described above and the production method of the present invention described above. A flavored and scented ice confection made of bubble-containing ice or ice slurry made by injecting flavored gas into fruit juice or fruit juice concentrated reduced liquid or fruitless beverage, The bubble content (volume ratio) of the ice or ice slurry is higher than 6% by volume.

The ice confectionery with a taste and aroma having a high ice gas content (volume ratio) of the present invention is characterized in that the gas content (volume ratio) of ice is higher than 6% by volume. Preferably, the gas content (volume ratio) of ice is 7 to 42% by volume, more preferably 8 to 33% by volume. When the gas content (volume ratio) of ice is less than 6% by volume, the content (gas content) of the ice confectionery flavored gas is not sufficient, and it is effective as an ice confectionery with a desired taste and aroma. There is a possibility that a new texture is not sufficiently obtained when bubbles are blown in the mouth when eating a frozen dessert having a short period and further coloring effect by bubbles and a gas content (volume ratio) of ice. On the other hand, the flavored and scented ice confectionery of the present invention has a high gas content (flavor content) with a flavor, and all forms from ice to ice slurry (shavet) are the above [II] [IIa]. Using the manufacturing apparatus shown in [IIb] (for example, by applying a voltage to the cooling member as shown in FIG. 12A, about 1.5 times (= 42% by volume) or more of gas more than when no voltage is applied). As a frozen dessert, the actual fruit taste and aroma can be realized.
[VI] Colored ice confectionery having a high ice gas content (volume ratio) The colored ice confectionery of the present invention uses the production apparatus of the present invention described above and uses the production method of the present invention described above. In addition, a colored (or even flavored) gas is injected into a colored liquid with water or food additives to make ice or ice making slurry, and colored air containing ice or ice slurry. Further, it is an ice confectionery (further fragrant), characterized in that the bubble content (volume ratio) of the ice or ice slurry is higher than 6% by volume.

  The colored (and even scented) ice confection having a high ice gas content (volume ratio) according to the present invention is characterized in that the gas content (volume ratio) of ice is higher than 6% by volume. It is. The gas content (volume ratio) of ice is preferably 7 to 42% by volume, more preferably 8 to 33% by volume. If the gas content (volume ratio) of ice is less than 6% by volume, the content (gas content) of the ice confectionery colored (and flavored) gas is not sufficient, and the desired color tone The effective period of ice confectionery colored on the surface is short, and the air bubbles in the mouth when eating ice confectionery that has the desired coloring effect (further aroma effect by fragrance) and ice gas content (volume ratio) due to bubbles There is a risk that you will not get enough fresh texture when you play. On the other hand, the colored (and scented) ice confectionery of the present invention has a high content (gas content) of colored (and further flavored) gas, and further, from ice to ice slurry (shavet). All the above-described forms are further reduced by using the manufacturing apparatus shown in the above [II] [IIa] [IIb] (for example, by applying a voltage to the cooling member as shown in FIG. It can be said that the gas can be contained by 5 times (= 42% by volume) or more, so that the actual fruit color and fragrance can be realized as frozen dessert.

  Hereinafter, the present invention will be described in detail using examples.

(Experimental example 1: Horizontal lower surface cooling of a flat cooling member → About the effect of increasing the content rate of contained ozone bubbles)
In Experimental Example 1, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the cooling surface 27a of the flat plate-shaped cooling member 27 is a horizontal lower surface (FIG. 2A2; Example 1), vertical. In the case of the side (FIG. 2A4; Comparative Example 1), the bubble content ratio in ice was measured. Here, in Example 1 and Comparative Example 1 of the present experimental example, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 is 30L ( Liter). The amount of the microbubble mixed water stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were reduced by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. The temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone Generation Stage First, in Example 1 and Comparative Example 1 of this experimental example, in the ozone generation stage (1), the apparatus 10 in which the cooling member 27 is installed as shown in FIG. 2A2 or FIG. 2A4 is used. First, ozone was generated by the discharge-type ozone generator 15 using oxygen supplied from the ozone source part (oxygen cylinder) 11 through the pipe 13 at an oxygen supply rate of about 0.45 L / min.

  The ozone concentration in the ozone-containing gas (= ozone + oxygen) generated in the ozone generation stage (1) was 7.5% by volume (catalog value) with respect to the supplied oxygen. The method for measuring the ozone concentration in the ozone-containing gas (= ozone + oxygen) relative to the supplied oxygen can be measured using the KI method.

(2) Bubble mixed water generation stage Next, in Example 1 and Comparative Example 1 of this experimental example, in the bubble mixed water generation stage (2), the ozone-containing gas generated in the ozone generation stage (1), Tap water supplied from the outside through the pipe 21 was introduced into the microbubble mixing device 23 to generate microbubble mixed water. The microbubble mixing device 23 was a pressure dissolution type device.

  Further, in this experimental example, when the required amount of microbubble mixed water (ozone water) is supplied to the water tank 33, the tap water supplied from the outside through the pipe 21 is stopped and from the water tank 33 through the pipe 19. The supplied (circulated) ozone water was introduced into the microbubble mixing device 23, and the generation of the microbubble mixed water was continued.

  Here, the amount of water supplied to the ozone-containing gas introduced into the microbubble mixing device 23 is appropriately adjusted so that the microbubble diameter distribution in the microbubble mixed water is 10 μm to 100 μm. went.

  Moreover, the distribution of the microbubble diameter in the microbubble mixed water obtained by the microbubble mixing apparatus (pressure dissolution type apparatus) 23 was in the range of 10 μm to 100 μm, and the average value of the microbubble diameter was 20 μm. The measurement method of the microbubble diameter and its average value can be measured using a laser diffraction scattering method.

  Further, by using the microbubble mixing device (pressure dissolution type device) 23, the dissolved ozone concentration (solubility of ozone in water) (average value) in the microbubble mixed water was a saturated concentration. In addition, the total concentration of dissolved ozone and the concentration of ozone in the microbubbles in the water mixed with microbubbles can realize a high bubble content for gas injection by using microbubbles, and a sufficient concentration of ozone in the bubbles can be obtained. The total concentration was 30 ppm or more. The measurement method of the ozone concentration in the microbubble mixed water can be measured using the KI method.

  Moreover, the average content (volume%) of the microbubbles in the water mixed with microbubbles was about 9.8% by volume. The measurement method of the content rate (volume%) of the microbubbles in the water mixed with microbubbles was measured using the measurement of the volume increase due to the inclusion of bubbles.

(3) Bubble mixed water supply stage (a) Example 1: When the cooling surface 27a of the flat cooling member 27 is a horizontal lower surface In the bubble mixed water supply stage (3) of Example 1, the bubble mixed water generation The tip of the supply pipe 25 of the bubble-mixed water is supplied so that the microbubble 29 can capture the microbubble-mixed water generated in the step (2) below the horizontal lower surface of the cooling surface 27a of the flat plate-like cooling member 27. 25a and the cooling member 27 were supplied to a water tank 33 disposed inside the tank so as to have the positional relationship shown in FIG. 2A2. The flow rate of the water mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

  In Example 1, as shown in FIG. 2A2, a flat plate-like cooling member 27 was horizontally installed on the upper portion of the water tank 33 (cooling member cooling surface angle 0 °; downward cooling). In particular, as shown in FIG. 2A2, when the required amount of microbubble mixed water is supplied to the water tank 33, the cooling surface 27a of the cooling member 27 is always below the water surface so that the cooling surface 27a is always below the water surface. The half was placed in the water. The tip 25a of the bubble-mixed water supply pipe 25 is located inside the water tank 33 and extends or contracts in the front-rear direction so that the microbubbles 29 can be trapped below the horizontal lower surface of the cooling surface 27a. The position was adjusted by bending and stretching.

(B) Comparative Example 1: When the cooling surface 27a of the flat cooling member 27 is a vertical lateral surface In the bubble mixed water supply stage (3) of Comparative Example 1, as in the existing manufacturing apparatus of Patent Document 1 and the like Instead of mixing microbubbles into the water injected into the container (water tank), the microbubble mixed water generated in the bubble mixed water generation step (2) is injected, and the periphery of the container (water tank 33) An experiment was conducted by imitating the structure of cooling from the beginning. Specifically, the water tank 33 is set so that the cooling surface angle of the flat plate-like cooling member 27 is 90 ° (= cooling from the periphery of the container; sideways cooling) in the water tank 33 so as to have the positional relationship shown in FIG. 2A4. The microbubble mixed water produced | generated at the said bubble mixed water production | generation stage (2) was supplied from the front-end | tip part 25a of the supply piping 25 to the water tank 33 arrange | positioned in the periphery (side surface) inside. The flow rate of the water mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

  The tip 25a of the bubble-mixed water supply pipe 25 is located below the side surface of the water tank 33 that faces the side surface of the water tank 33 on which the flat plate-like cooling member 27 is disposed. The position was adjusted by expanding or contracting in the front-rear direction or bending in the vertical and horizontal directions so that it could be evenly (uniformly) dispersed.

(4) Ozone ice generation stage (a) Example 1: When the cooling surface 27a of the flat cooling member 27 is a horizontal lower surface By the bubble mixed water supply step (3), the cooling surface 27a of the cooling member 27 is placed below the cooling surface 27a. With the microbubbles captured, ethylene glycol is used as a refrigerant (brine) from the refrigerant circulation device 37 in the circulation flow path 35 inside the cooling member 27, and the temperature of the refrigerant is adjusted to -20 to -22 ° C. By circulating, the cooling surface 27a of the cooling member 27 was cooled to -13 ° C., and ozone ice containing bubbles was generated on the cooling surface side for an ice making time of 40 minutes.

(B) Comparative Example 1: When the cooling surface 27a of the flat cooling member 27 is a vertical horizontal surface By the bubble mixed water supply step (3), the microbubbles 29 are substantially evenly (uniformly) all over the water tank 33. In a dispersed state, ethylene glycol is used as the refrigerant from the refrigerant circulation device 37 in the circulation flow path 35 inside the cooling member 27, the temperature of the refrigerant is adjusted to -20 to -22 ° C, and the refrigerant is circulated. 27 cooling surfaces 27a were cooled to −6.8 ° C., and the ice making time was 40 minutes, and ozone ice containing bubbles was generated on the cooling surface side.

(4a) Exhaust process In Example 1 and Comparative Example 1 of this experimental example, during the ozone ice generation stage (4), the microbubbles 29 in the water mixed with microbubbles float on the liquid surface as a reuse process. Without supplying gasified components from the water tank 33 to the ozone generator 15 through the pipe 43, the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 float on the liquid surface and serve as an exhaust process. The experiment was conducted while exhausting the converted components from the water tank 33 through the exhaust pipe 41 to the outside of the system.

  The result of measuring the bubble content (volume%) in the ozone ice 39 obtained in Example 1 of Comparative Example 1 and Comparative Example 1 is shown in the drawing (graph) of FIG. 3A.

  3A, the cooling surface 27a of the cooling member 27 has a horizontal lower surface (horizontal wall) about 2.5 times larger than the vertical lateral surface (vertical wall), and the bubble content (ratio) in the ozone ice 39 is larger. From the confirmed FIG. 3A, in the production apparatus 10 shown in FIG. 1, the bubble content (ratio) of the ozone ice 39 is 11% by volume on the horizontal lower surface (horizontal wall), which is about twice that of the previous Patent Document 1, It has been confirmed that the effect of increasing the content of bubbles containing ozone (gas) is remarkably obtained about four times as much as when the technique described as the prior art in Patent Document 1 is used.

(Experimental example 2: About the bubble content rate of ice by the cooling surface angle of a flat cooling member)
Also in the present experimental example 2, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the cooling with the flat cooling member 29 as the cooling member 29 (cooling surface angle is 0 ° = horizontal wall) is used. Cooling surface angle (°) from member 29 to cooling member 29 with cooling surface angles of 10 °, 15 °, 20 °, 25 °, 30 °, 45 ° and even vertical (cooling surface angle is 90 ° = vertical wall) ) Was measured as to how the bubble content (volume%) in the ozone ice 39 changed. The results are shown in FIG. 3B, and drawings showing a photograph of the obtained ozone ice from a plane and a photograph from a side surface (cross section) are shown in FIGS. 4 to 11. Here, also in this experiment example, the water tank 33 is a closed water tank having a cubic shape and a lid 33a that can be opened and closed, and the water tank 33 has an internal volume of 20 L (liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

  In Experimental Example 2, among the experimental conditions of Experimental Example 1, the temperature of the cooling surface of the cooling member of the experimental device was set to -13 ° C. (Example 1) and −6.8 ° C. (Comparative Example 1). Was changed to about -7 to -13 ° C. The reason why the temperature of the cooling surface varies is that the heat transfer coefficient near the cooling surface changes due to the difference in the cooling surface angle.

  In this Experimental Example 2, oxygen gas microbubbles were used instead of ozone gas microbubbles. However, when the cooling surface angle was 0 °, air microbubbles were used. The experimental conditions are shown in Table 1 below. In this example, as a preliminary experiment, an oxygen gas microbubble and an air microbubble were used, and a supplementary experiment of Example 1 of Comparative Example 1 and Comparative Example 1 was performed. As a result, the bubble content of ozone ice when using the ozone gas microbubbles of Example 1 of Experimental Example 1 and Comparative Example 1 (11% by volume in Example 1, 6% by volume in Comparative Example 1), and oxygen gas Since it was confirmed that there was no difference in the bubble content of oxygen ice when using microbubbles (11% by volume in the follow-up experiment of Example 1 and 6% by volume in the follow-up experiment in Comparative Example 1), this experiment example In No. 2, oxygen gas microbubbles and air microbubbles are simply used. However, in Experimental Example 2, since air was used when the cooling surface angle was 0 ° and the gas flow rate to the microbubble mixing device 23 (see Table 1 below) was not limited, As a result of supplying a large amount of gas (air), there was a large hole on the surface as shown in FIG. 4, and the measurement result of the bubble content rose due to the effect of the hole (bubbles of air ice It is considered that the content is 28% by volume. As evidence, the mass of ice is markedly lower than the experimental examples at other cooling surface angles as shown in Table 1 by supplying a large amount of gas, and air is used when the cooling surface angle is 0 °. The bubble content of air ice should be limited to the reference value.

(1) Bubble mixed water production | generation stage In this experiment example, the bubble mixed water production | generation stage was performed, without performing the ozone generation stage of Experimental example 1. FIG.

  In this Experimental Example 2, the oxygen cylinder 11 is connected to the pipe 17 using the manufacturing apparatus 10 in which the cooling member 27 is installed while changing the cooling surface angle from 0 to 90 ° as shown in FIGS. 2A2, 2A3, and 2A4. Oxygen supplied through the pipe 17 at an oxygen supply rate of 0.45 L / min and tap water supplied from the outside through the pipe 21 are introduced into the microbubble mixing device 23 to generate microbubble mixed water. I let you. However, when the cooling surface angle is 0 °, air is supplied through the pipe 19 without restricting the air supply amount using the pump (not shown) instead of the oxygen cylinder 11 and supplied from the outside through the pipe 21. The tap water was introduced into the microbubble mixing device 23 to generate microbubble mixed water. The microbubble mixing device 23 was a pressure dissolution type device.

  Further, in this experimental example 2, when a necessary amount of microbubble mixed water is supplied to the water tank 33, the tap water supplied from the outside through the pipe 21 is stopped and supplied from the water tank 33 through the pipe 19 (circulation). The air-dissolved water or oxygen-dissolved water is introduced into the microbubble mixing device 23 and the generation of the microbubble mixed water was continued.

  Here, the amount of water supplied to the oxygen gas introduced into the microbubble mixing device 23 is adjusted appropriately so that the microbubble diameter distribution in the microbubble mixing water is 10 μm to 100 μm. It was. On the other hand, the amount of water supplied to the air introduced into the microbubble mixing device 23 was also adjusted appropriately so that the distribution of the microbubble diameter in the microbubble mixed water was 10 μm to 100 μm.

  Moreover, the distribution of the microbubble diameter in the microbubble mixed water obtained by the microbubble mixing apparatus (pressure dissolution type apparatus) 23 was in the range of 10 μm to 100 μm, and the average value of the microbubble diameter was 20 μm. The microbubble diameter and the average value were measured in the same manner as in Experimental Example 1.

  Further, by using the microbubble mixing device (pressure dissolution type device) 23, the dissolved oxygen (solubility of oxygen in water) (average value) in the water mixed with microbubbles was a saturated concentration. Dissolved air in microbubble-mixed water (solubility of air in water) (average value) was also saturated because a large amount of air was supplied. The method for measuring the dissolved oxygen or air concentration in the microbubble-containing water was the same as in Experimental Example 1.

  Moreover, the average content (volume%) of oxygen microbubbles in the water mixed with microbubbles was about 9.8% by volume. On the other hand, in a large amount of supplied air, the content (volume%) of air microbubbles in the water mixed with microbubbles was about 11 volume%. The method for measuring the content (volume%) of oxygen or air microbubbles in the water mixed with microbubbles was the same as in Experimental Example 1.

(2) Bubble mixed water supply stage In the bubble mixed water supply stage (2), the cooling surface angle of the flat cooling member 27 is 0 ° using the microbubble mixed water generated in the bubble mixed water generation stage (1). (= Horizontal wall) The tip of the supply pipe 25 of the bubble-mixed water 25 so that the microbubbles 29 can be captured below the cooling surface up to 10 °, 15 °, 20 °, 25 °, 30 °, and 45 °. 25a and the cooling member 27 were supplied to a water tank 33 disposed inside the tank as shown in FIGS. 2A2 and 2A3, for example. The flow rate of the water mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

(A) When the cooling surface angle of the flat cooling member 27 is 0 ° to 45 ° As shown in FIGS. 2A2 and 2A3, the cooling surface angle of the flat cooling member 27 is set to 0 ° to 45 °. It was tilted to 45 ° (specifically, 0 ° (= horizontal wall), 10 °, 15 °, 20 °, 25 °, 30 °, 45 °; all cooled downward) and installed on the upper part of the water tank. In particular, as shown in FIGS. 2A2 and 2A3, when the necessary amount of microbubble-mixed water is supplied to the water tank 33, the flat cooling member 27 so that the cooling surface 27 a of the cooling member 27 is always below the water surface. Was placed at a position where it was immersed substantially below the liquid level. The tip 25a of the bubble-mixed water supply pipe 25 is located below the water tank 33, and the microbubbles 29 are provided below the cooling surface 27 in which the cooling surface angle of the cooling member is inclined from 0 ° to 45 ° (downward cooling). The position was adjusted by expanding and contracting in the front-rear direction or bending it up and down and left and right.

(B) When the cooling surface angle of the flat plate-like cooling member 27 is 90 ° In the case where the cooling surface angle of the flat plate-like cooling member 27 is inclined to 90 ° (lateral cooling), as shown in FIG. 33 was installed inside. Specifically, it was set as the structure similar to the comparative example 1 of the experiment example 1. FIG. That is, in the bubble-mixed water supply stage (2), in the same manner as in the existing manufacturing apparatus such as Patent Document 1, the bubble-mixed water is replaced by mixing microbubbles into the water injected into the container (water tank). Experiments were performed by simulating a configuration in which the microbubble-mixed water generated in the generation stage (2) was injected and cooled from around the container (water tank 33). Specifically, the water tank 33 is set so that the cooling surface angle of the flat plate-like cooling member 27 is 90 ° (= cooling from the periphery of the container; sideways cooling) in the water tank 33 so as to have the positional relationship shown in FIG. 2A4. The microbubble mixed water produced | generated at the said bubble mixed water production | generation stage (1) was supplied from the front-end | tip part 25a of the supply piping 25 to the water tank 33 arrange | positioned in the periphery (side surface) inside. The flow rate of the water mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

  The tip 25a of the bubble-mixed water supply pipe 25 is located below the side surface of the water tank 33 that faces the side surface of the water tank 33 on which the flat plate-like cooling member 27 is disposed. The position was adjusted by expanding or contracting in the front-rear direction or bending in the vertical and horizontal directions so that it could be evenly (uniformly) dispersed.

(3) Ozone ice generation stage (a) When the cooling surface angle of the flat cooling member 27 is 0 ° to 45 ° By the bubble mixed water supply step (2), microbubbles are formed under the cooling surface 27a of the cooling member 27. In the captured state, ethylene glycol is used as the refrigerant from the refrigerant circulation device 37 in the circulation flow path 35 inside the cooling member 27, the temperature of the refrigerant is adjusted to -20 to -22 ° C, and the refrigerant is circulated. 27 cooling surfaces 27a were cooled to −7.5 to −13 ° C., and ice-making time was 40 minutes, and oxygen-containing or air-containing ice containing bubbles was generated on the cooling surface side.

(B) When the cooling surface angle of the flat cooling member 27 is 90 ° In the bubble mixed water supply step (2), the microbubbles 29 are cooled substantially uniformly (uniformly) throughout the water tank 33. Using ethylene glycol as the refrigerant from the refrigerant circulation device 37 in the circulation channel 35 inside the member 27, adjusting the temperature of the refrigerant to −20 to −22 ° C. and circulating it, the cooling surface 27a of the cooling member 27 is − The mixture was cooled to 6.8 ° C., and the ice-making time was 40 minutes, thereby generating oxygen-containing ice containing bubbles on the cooling surface side.

(4a) Exhaust process Also in this experimental example, during the ozone ice generation stage (3), the component in which the microbubbles 29 in the microbubble mixed water float and gasify on the liquid surface is reused in the water tank 33 as a reuse process. Without supplying the ozone generator 15 from the pipe 15 through the pipe 43, as an exhausting step (4 a), the components in which the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 are floated on the liquid surface and gasified are stored in the water tank. The experiment was conducted while exhausting the gas from outside 33 through the exhaust pipe 41.

  The results of measuring the bubble content (volume%) in the oxygen-containing ice or the air-containing ice obtained by changing the cooling surface angle of the flat plate-like cooling member 27 from 0 ° to 90 ° in Experimental Example 2, This is shown in the drawing (graph) of FIG. 3B. Moreover, the photograph of the ice produced | generated at that time is shown to FIGS.

  In Table 1, “−” in the column of the gas flow rate [L / min] when the cooling surface angle is 0 ° means that air is supplied.

  FIG. 3B shows that the bubble content decreases as the cooling surface angle increases. At 0 °, it is about 28%, but at 90 °, it is about 7%. However, when looking at the drawing representing the 0 ° ice photograph in FIG. 4, there is a large hole on the surface, and the measurement result of the bubble content seems to have increased due to the influence of the hole. However, when the cooling surface angle is gradually inclined, as shown in FIGS. 5 to 8, large holes on the surface tend to gradually decrease. When the tendency is observed in detail, when the cooling surface angle is 10 to 15 °, the bubble content rate is greatly increased as compared to the cooling surface angle of 20 ° (see FIG. 3B). When the cooling surface angle is 20 to 45 °, the bubble content is hardly changed. When the cooling surface angle is 90 °, the bubble content is lower than that of the cooling surface angle of 20 to 45 °. In addition, the white place in the ice of the drawing showing the photograph of FIGS. 4-11 is a containing bubble. Therefore, from FIG. 3B, considering the bubble content, it is considered that the cooling surface angle is 10 to 15 °. The bubble content at that angle is about 22% by volume. This value is twice as large as the bubble content of 11% by volume at the cooling surface angle of 0 ° in Experimental Example 1 (and this Experimental Example 2), and is about four times as large as 6% by volume in Patent Document 1. That's it.

(Experimental example 3; Application of voltage to the cooling surface of the flat cooling member ⇒ Increase / suppression effect of the average increase rate of ozone microbubbles on the cooling surface and the ozone bubble content ratio in ozone ice on the cooling surface)
In Experimental Example 3, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the cooling surface 27a of the flat plate-like cooling member 27 is a horizontal lower surface (FIG. 2A2), and the vertical side surface is used. In FIG. 2A4, the relationship between the applied voltage (0 to 400V) to the cooling surface 27a of the cooling member 27 and the average increase rate of ozone microbubbles on the cooling surface in ozone water, and (the ratio of bubbles contained in ozone ice) / The ratio of (microbabil content on the cooling surface in ozone water) was measured. Here, also in this experiment example, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 was 30 L (liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone Generation Stage First, in this Experimental Example 3, the ozone generation stage (1) was performed in the same manner as in Example 1 and Comparative Example 1 of Experimental Example 1.

(2) Bubble mixed water production | generation stage Next, in this Experimental example 3, it carried out similarly to Example 1 of Experimental example 1, and the comparative example 1, and implemented the bubble mixed water production | generation stage (2).

(3) Bubble mixed water supply stage Next, in this Experimental Example 3, the bubble mixed water supply stage (3) was performed in the same manner as in Example 1 and Comparative Example 1 of Experimental Example 1.

(4) Ozone Ice Generation Stage Next, in Experimental Example 3, the ozone ice generation stage (4) was performed in the same manner as in Example 1 and Comparative Example 1 of Experimental Example 1. However, in Experimental Example 2, the DC power supply 47 is connected to the cooling member 27 during the ice making time (40 minutes), and voltages of 0V, 100V, 200V, 300V, and 400V are respectively applied to the cooling surface 27a of the cooling member 27. This was applied to generate ozone ice containing bubbles on the cooling surface side.

(4a) Exhaust Step Next, in this Experimental Example 3, in the same manner as in Example 1 of Comparative Example 1 and Comparative Example 1, without performing a reuse step during the ozone ice generation stage (4), The experiment was conducted by performing the exhaust process (4a).

  In Experiment 3, the relationship between the applied voltage (0 to 400 V) to the cooling surface 27a of the cooling member 27 and the average increase rate of ozone microbubbles on the cooling surface in ozone water was measured, and the obtained result is shown in FIG. 12A. It was. Moreover, when the applied voltage to the cooling surface 27a of the cooling member 27 is 400 V, the relationship of the ratio of (bubble content in ozone ice) / (microbavir content on the cooling surface in ozone water) is measured and obtained. The results are shown in FIG. 12B. FIG. 12A shows only an example in which an experiment was performed in the same manner as in Example 1 of Experimental Example 1.

  From FIG. 12A, when the cooling surface 27a of the flat cooling member 27 is a horizontal lower surface (cooling surface angle 0 °; lower is cooled) (FIG. 2A2), the magnitude of the applied voltage is increased from 0V to 400V (change) It was confirmed that the amount of ozone microbubbles on the cooling surface 27a of the cooling member 27 in ozone water increased by 50% by volume or more. Further, from FIG. 12B, the cooling surface 27a of the flat plate-like cooling member 27 has a lower horizontal surface (horizontal wall) than a vertical horizontal surface (vertical wall) (bubble content in ozone ice) / (in ozone water). It was confirmed that the ratio of microbavir content on the cooling surface was about 1.3 times larger. In particular, on the horizontal lower surface (horizontal wall), the vertical axis exceeds 100% (average is about 130%), so the bubbles contained in ozone ice than the ozone microbubble content on the cooling surface in ozone water It can be confirmed that the rate is larger. This is because the ozone microbubbles increased under the cooling surface in the ozone water can be efficiently captured (contained) in the ozone ice, and remain below the cooling surface 27a for a longer time without floating on the liquid surface. It can be said that it is possible to keep. On the other hand, on the vertical horizontal surface (vertical wall), the vertical axis is significantly lower than 100% (on average, it is less than 50%), so the ozone microbubble content in the vicinity of the cooling surface in ozone water It can be confirmed that the bubble content in ozone ice is smaller. This is a structure in which ozone microbubbles are evenly dispersed in ozone water, so it is difficult to collect (supplement) microbubbles in the vicinity of the cooling surface, and to keep the dispersed microbubbles in the vicinity of the cooling surface. As a result of allowing the float to easily rise above the liquid level, the bubble rises while moving with a levitation force and is less likely to be captured as compared to a state where the bubble stays stable and is easily captured. Therefore, it can be said that the bubbles that can be contained (supplemented) in ozone ice are extremely limited.

(Experimental example 4: Ozone microbubble mixed water injection method)
In this experimental example 4, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, when the cooling surface 27a of the flat cooling member 27 is a horizontal lower surface (FIG. 2A2), ozone microbubble mixed water The state of change of the bubble diameter in the obtained ozone ice 39 was measured by continuously or intermittently performing the injection method. Here, in Experimental Example 4, as in Experimental Example 1, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 is 30L ( Liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone generation stage First, in this Experimental Example 4, the ozone generation stage (1) was performed in the same manner as in Example 1 of Experimental Example 1.

(2) Bubble mixed water production | generation stage Next, in this Experimental example 4, it carried out similarly to Example 1 of Experimental example 1, and implemented the bubble mixed water production | generation stage (2).

(3) Bubble mixed water supply stage Next, in Experimental Example 4, the bubble mixed water supply stage (3) was performed in the same manner as in Example 1 of Experimental Example 1. However, in this experimental example, as Example A for continuous injection, Example B for repeating 15-minute injection 1-minute stop, and Example C for repeating 30-minute injection 1-minute stop as examples of intermittent injection And went. The operations of injection, stop, injection (restart),... Are not shown in FIG. 1, but linked open / close valves are provided in the pipes 13, 17, 19 (or 21) and 25. When the injection of ozone microbubble mixed water was started (started), all these valves were controlled to open in conjunction with each other. Next, when stopping the injection of ozone micro-bubble mixed water, all these valves are interlocked and, after that, when restarting (restarting) the injection of ozone micro-bubble mixed water, all of these valves are closed. The valve was controlled to open in conjunction with the injection of ozone microbubble mixed water intermittently.

(4) Ozone Ice Generation Stage Next, in Experimental Example 4, the ozone ice generation stage (4) was performed in the same manner as in Example 1 of Experimental Example 1.

(4a) Exhaust Process Next, in Experimental Example 4, as in Example 1 of Experimental Example 1, the exhaust process (4a) is performed without performing the reuse process during the ozone ice generation stage (4). ) To conduct the experiment.

  In the present Example 4, the ozone microbubble mixed water injection method is made continuous, so that the effect of increasing the amount of ozone bubbles is recognized in the inclusion in the obtained ozone ice 39 as compared with the case where it is intermittent. It was. On the other hand, the ozone in the ozone ice 39 obtained is compared with the case where it is made continuous by intermittently injecting the ozone microbubble mixed water (the ozone bubble diameter (average value) 120 μm in the ozone ice)). It was confirmed that the bubble diameter can be changed (the ozone bubble diameter (average value) in the ozone ice can be arbitrarily controlled in the range of 70 to 135 μm by changing the stop time and the number of stops). In addition, when performing intermittently, it has confirmed that the ozone bubble diameter (average value) in ozone ice was controllable other than the said range by further changing stop time and the frequency | count of a stop. From the above, it was confirmed that the bubble diameter in ozone ice could be controlled to some extent by the injection method of ozone microbubble mixed water. Therefore, depending on the application, the rate at which air bubbles trapped in the ice gradually melt during the process of melting the ozone ice 39 and release the internal ozone gas (release rate) is the type of fresh food and transportation. It turned out that it can adjust suitably according to time etc.

(Experimental example 5: Exhaust ozone / oxygen gas (component which microbubble 29 floated on the liquid surface and gasified): About reuse after moisture removal)
In Experimental Example 5, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the microbubbles 29 in the microbubble mixed water are used as the reuse step (4a) during the ozone ice generation stage (4). After the moisture is removed from the water tank 33 by the moisture removing device 45 provided on the path 43 of the pipe 43 from the water tank 33, the component gasified and gasified on the liquid surface is supplied (reused) to the ozone generator 15 through the pipe 43. The experiment was conducted while measuring the concentration of dissolved ozone in the obtained ozone ice 39 and the concentration of ozone gas in the contained bubbles. Here, in Experimental Example 5, as in Experimental Example 1, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 is 30L ( Liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. The cooling member 27 is a copper flat plate (longitudinal 8 cm, lateral 8 cm, thickness 1 cm) excellent in thermal conductivity, and the cooling surface 27a of the cooling member 27 has an area of 1 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone generation stage First, in Experimental Example 5, the ozone generation stage (1) was performed in the same manner as in Example 1 of Experimental Example 1.

(2) Bubble mixed water production | generation stage Next, in this Experimental example 5, it carried out similarly to Example 1 of Experimental example 1, and implemented the bubble mixed water production | generation stage (2).

(3) Bubble mixed water supply stage Next, in Experimental Example 5, the bubble mixed water supply stage (3) was performed in the same manner as in Example 1 of Experimental Example 1.

(4) Ozone Ice Generation Stage Next, in Experimental Example 5, the ozone ice generation stage (4) was performed in the same manner as in Example 1 of Experimental Example 1.

(4a) Reuse process Next, in this experiment example 4, it experimented by implementing a reuse process, without implementing an exhaust process in the said ozone ice production | generation stage (4).

  Specifically, as the exhaust process, the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 are floated on the liquid surface and gasified without exhausting the component from the water tank 33 through the exhaust pipe 41 to the outside of the system. As a reuse step (4a), the microbubbles 29 in the microbubble-mixed water float on the liquid surface and can be freely attached to and detached from a part of the path of the pipe 43 that supplies gasified components from the water tank 33 to the ozone generator 15. An enlarged diameter portion 43a is provided, and a Peltier element 45a is arranged at the enlarged diameter portion 43, and the gasified component is cooled and dehumidified by the Peltier element 45a to remove moisture in the gasified component. Later, an experiment was conducted while supplying (reusing) the ozone generator 15 through the pipe 43. The flow rate of the gasified component (dry component after moisture removal) supplied (reused) to the ozone generator 15 through the pipe 43 is about 1 L / min, and is supplied to the ozone generator 15 through the pipe 13. The oxygen supply amount was adjusted to about 4 L / min, and the supply amount of the entire gas component supplied to the ozone generator 15 through both the pipes 13 and 43 was adjusted to 5 L / min. The dissolved ozone concentration in the obtained ozone ice 39 and the concentration of ozone gas in the contained bubbles were measured.

  In the fifth embodiment, during the ozone ice generation step (4), the recycle process is performed without performing the exhaust process, so that the ozone ice 39 obtained can be obtained as compared with the case where the exhaust process is performed. Increased concentration of dissolved ozone and the concentration of ozone gas in the contained bubbles were observed.

  Specifically, while the bubble content in the ozone ice 39 obtained in Example 1 of Experimental Example 1 was 11% by volume, the bubble content in the ozone ice 39 obtained in Experimental Example 5 was included. The rate was also almost the same (about 11% by volume), although it was difficult to compare directly because the cooling areas were different.

  In this Experimental Example 5, the concentration of ozone generated by the ozone generator 15 can be increased by reusing the microbubbles 29 in the bubble-mixed water that floats on the liquid surface and does not exhaust the gasified components. Enhanced. That is, the concentration of ozone gas in the component gasified by floating the microbubbles 29 in the bubble-containing water is not increased or decreased even after passing through the ozone generator 15, and the microbubbles 29 in the bubble-containing water float on the liquid level. The microbubble mixed water supplied to the pipe 25 from the ozone gas generator 15 through the microbubble mixing device 23 by the ozone in the gasified component and the ozone gas newly generated from the oxygen supplied from the pipe 13. The ozone gas concentration in the bubble 29 is increased. The ozone dissolved in the ozone water of the microbubble mixed water has a saturated concentration and is the same as in Experimental Example 1. Therefore, the microbubbles 29 containing the ozone gas thus highly concentrated are supplied to the water tank 33 and taken into the ozone ice 39 by ice making, so that the dissolved ozone concentration in the ozone ice 39 and the concentration of ozone gas in the contained bubbles are obtained. It is easily guessed that the effect of increasing the above was obtained. Therefore, depending on the application, even if the air bubbles trapped in the ice ice 39 gradually melt and release the internal ozone gas (release rate) relatively slowly, It was found that the food can be sufficiently cooled, sterilized and deodorized, and can provide ozone ice suitable for long-term storage and transportation.

(Experimental example 6; When using tap water: Ozone ice using water from which chlorine has been removed by a chlorine gas removing device)
First, as preliminary experiment 6a of Experimental Example 6, tap water and tap water from which chlorine was removed by ultraviolet rays after being left for 2 days (48 hours) were respectively the same as Example 1 of Experimental Example 1. Then, the ozone generation stage (1) and the bubble mixed water generation stage (2) were carried out. After collecting the obtained bubble-mixed water and injecting ozone (= because the mixing time in the micro-bubble mixing device 23 is short, after collecting the bubble-mixed water), with the passage of time, bubble mixing generated using tap water Dissolved ozone concentration in water and ozone gas concentration in microbubbles (= “Dissolved ozone concentration in bubble-mixed water and ozone gas concentration in microbubbles” is simply referred to as “total ozone concentration”), and left for 2 days by ultraviolet rays The total ozone gas concentration in the bubble mixed water produced | generated using the tap water from which chlorine was removed was measured, and the obtained result is shown in FIG. It should be noted that the dimensionless ozone water concentration on the vertical axis in FIG. 13 [−] = (total ozone gas concentration in bubble-mixed water generated using tap water that has been left for two days to remove chlorine by ultraviolet rays) / (tap water This represents the total ozone gas concentration in the bubble-containing water generated by the use. From the results shown in FIG. 4, with the passage of time, bubbles generated using tap water from which chlorine was removed by ultraviolet rays after being left for 2 days against the total ozone gas concentration in bubble-containing water generated using tap water. The total ozone gas concentration in the mixed water increases, and after about 4 hours, the total ozone gas concentration in the bubble mixed water generated by using tap water that has been left for about 2.5 times for 2 days to remove chlorine by ultraviolet rays is better. high. Therefore, it was confirmed that it is more effective for ice making to use tap water used after removing chlorine. Based on the above results, in the following Experimental Example 6, ice making was performed by a manufacturing method using the ozone ice manufacturing apparatus 10 of the present invention.

In Experimental Example 6, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the ozone generation apparatus 15 is supplied from the water tank 33 as the chlorine removal step (2a) in the bubble mixed water generation stage (2). The experiment was conducted while removing chlorine from the water using a chlorine removing device 49 installed on the path of the pipe 19 for supplying the water to be supplied and / or on the path of the pipe 21 for supplying the tap water supplied from the outside. Thus, the ozone concentration in the bubbles contained in the ozone ice 39 when the chlorinated tap water is used with respect to the ozone concentration in the bubbles contained in the ozone ice 39 when the tap water is used without removing the chlorine. The proportion of was measured. Here, in Experimental Example 5, as in Experimental Example 1, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 is 30L ( Liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone Generation Stage First, in Experimental Example 6, the ozone generation stage (1) was performed in the same manner as in Example 1 of Experimental Example 1.

(2) Bubble mixed water production | generation stage Next, in this experiment example 6, it carried out similarly to Example 1 of experiment example 1, and implemented the bubble mixing water production | generation stage (2). In Experimental Example 6, a chlorine removal device 49 installed on the path of the pipe 21 for supplying tap water supplied from the outside as a chlorine removal step (2a) in the bubble mixed water generation stage (2). The experiment was carried out while removing chlorine from water.

(3) Bubble mixed water supply stage Next, in Experimental Example 6, the bubble mixed water supply stage (3) was performed in the same manner as in Example 1 of Experimental Example 1.

(4) Ozone Ice Generation Stage Next, in Experimental Example 6, the ozone ice generation stage (4) was performed in the same manner as in Example 1 of Experimental Example 1.

(4a) Exhaust Step Next, in this Experimental Example 3, in the same manner as in Example 1 of Comparative Example 1 and Comparative Example 1, without performing a reuse step during the ozone ice generation stage (4), The experiment was conducted by performing the exhaust process (4a).

  In Experimental Example 6, the chlorine removal step (2a) was performed while removing chlorine in tap water, and the bubbles contained in ozone ice 39 when tap water was used without removing chlorine. The ratio of ozone concentration in bubbles contained in ozone ice 39 when using chlorine-free tap water with respect to ozone concentration (Example 1 of Experimental Example 1) was measured. As a result, the ratio of ozone concentration in the bubbles contained in ozone ice 39 when chlorine-free tap water is used is about 2.5 times higher. For ice making, tap water used after removing chlorine is used. It was confirmed that the use was more effective. When using tap water, install a chlorine gas removal device (for example, with ultraviolet irradiation) and use tap water from which chlorine has been removed, so that the cost can be significantly reduced compared to using distilled water. I understood. Moreover, since the decrease in ozone due to chlorine was suppressed, it was confirmed that the effect of increasing the dissolved ozone concentration in the obtained ozone ice 39 and the concentration of ozone gas in the contained bubbles was obtained.

(Experimental Example 7: Use of ozone ice slurry generated from water)
In Experimental Example 7, in the manufacturing method using the ozone ice slurry manufacturing apparatus 10A shown in FIG. 1, the cooling surface 27a of the flat cooling member 27 is placed on the horizontal lower surface (FIG. 2A2) as in Example 1 of Experimental Example 1. ), And the bubble content in the ice slurry generated from water was measured.

Here, also in this experiment example, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 was 30 L (liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease with time, and it decreased to 2.5 to 3.0 ° C. during the experiment (40 minutes).

(1) Ozone generation stage First, in Experimental Example 7, the ozone generation stage (1) was performed in the same manner as in Example 1 of Experimental Example 1.

(2) Bubble mixed water production | generation stage Next, in this Experimental example 7, it carried out similarly to Example 1 of Experimental example 1, and implemented the bubble mixed water production | generation stage (2).

(3) Bubble Mixed Water Supply Stage Next, in Experimental Example 7, the bubble mixed water supply stage (3) was performed in the same manner as in Example 1 of Experimental Example 1.

(4) Ozone Ice Generation Stage Next, in Experimental Example 7, the ozone ice generation stage (4) was performed in the same manner as in Example 1 of Experimental Example 1.

(4a) Exhaust Process In Experimental Example 7, the exhaust process (4a) was performed during the ozone ice generation stage (4) without performing the reuse process, as in Example 1 of Experimental Example 1. The experiment was conducted.

(5) Ice slurry stage In the seventh embodiment, the ozone ice 39 generated on the cooling surface 27a of the cooling member 27 obtained in the ozone ice generation stage (4) is converted into the harvest method (here, the inside of the cooling member 27). The ozone ice 39 peeled off by a heat medium (a method in which ethylene glycol was used for the heat medium) at −20 to −22 ° C. from the refrigerant circulation device 37 in the circulation channel 35 of An experiment was carried out to generate an ozone ice slurry by carrying out a step (ice slurry step) of scraping and slurrying using a cutting device (not shown).

  It was confirmed that the obtained ozone ice slurry had fluidity and good heat load followability. The bubble content in the ozone ice before the ice slurry stage is 11% by volume (see Example 1 of Experimental Example 1), and the bubble content in the ozone ice slurry after the ice slurry stage is about the same as that of ozone ice. Met. Furthermore, the total of the dissolved ozone concentration in the ozone ice slurry and the bubble-containing ozone concentration is about 25 ppm (about the same as ozone ice) at present. If the dissolved ozone concentration of ozone ice and the total of the bubble-containing ozone concentration are about 1 to 5 ppm, the bactericidal and deodorizing action can be sufficiently exerted by the bubble-containing ozone and the ozone water when dissolved. The ozone gas concentration in the bubbles of the ozone ice slurry was similar to that of ozone ice.

(Experimental Example 8: Use of ozone ice slurry generated from aqueous solution)
In the present experimental example 8, in the manufacturing method using the ozone ice slurry manufacturing apparatus 10A shown in FIG. 1, the cooling surface 27a of the flat cooling member 27 is placed on the horizontal lower surface (FIG. 2A2) as in the first embodiment of the experimental example 1. ) And the bubble content in the ozone ice slurry produced from the aqueous solution was measured.

Here, also in this experiment example 8, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 was 30 L (liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of the propylene glycol (PG) -containing ozone water supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease over time, and during the experiment (40 minutes), depending on the propylene glycol content concentration, It had fallen to about -2 to -12 degreeC (all are not frozen).

(1) Ozone generation stage First, in Experimental Example 8, the ozone generation stage (1) was performed in the same manner as in Example 1 of Experimental Example 1.

(2) Bubble mixed aqueous solution production | generation stage Next, in this Experimental example 8, the bubble mixed aqueous solution production | generation stage (2) was implemented similarly to the bubble mixed water production | generation stage (2) of Example 1 of Experimental example 1. FIG. In Experimental Example 8, the following additive supply step (2a) was further performed during the bubble-containing aqueous solution generation step (2).

(2a) Additive supply step In this Experimental Example 8, in the bubble mixed aqueous solution generation step (2), the ozone-containing gas generated in the ozone generation step (1), and tap water supplied from the outside through the pipe 21 Further, as an additive supply step (2a), propylene glycol (PG; an additive capable of forming an ozone ice slurry) supplied from the storage unit 51 through a pipe 55 provided with a flow rate adjusting valve 53 is supplied to the microbubble mixing device 23. It was introduced to produce an aqueous solution containing microbubbles. The microbubble mixing device 23 was a pressure dissolution type device.

  At this time, the supply amount of PG with respect to the supply amount (flow rate) of water supplied to the mixing device 23 is a predetermined ratio, specifically, 5% by volume, 10% by volume, 15% by volume, and 20% by volume. % And 25% by volume.

  Here, in the bubble-containing aqueous solution generation step (2), the supply amount of water supplied to the ozone-containing gas introduced into the micro-bubble mixing device 23 is such that the distribution of the micro-bubble diameter in the micro-bubble mixed water is 10 μm to It adjusted suitably so that it might be set to 100 micrometers. Further, with respect to the supply amount (flow rate) of the tap water supplied through the pipe 21, the supply amount of the tap water (the flow rate adjustment valve 53 on the pipe 55 is adjusted so that the PG supply amount at the predetermined ratio described above is obtained. The flow rate was adjusted so that a predetermined amount of PG was supplied.

  Also in this experimental example, when the required amount of aqueous solution containing microbubbles is supplied to the water tank 33, the supply of tap water supplied from the outside through the pipe 21 and PG from the pipe 55 is stopped, and the water tank 33 is also supplied. The microbubble mixed aqueous solution supplied (circulated) through the pipe 19 was introduced into the microbubble mixing device 23, and the generation of the microbubble mixed aqueous solution was continued.

  Therefore, when the microbubble mixed aqueous solution once adjusted to a predetermined PG concentration by adding PG to the tap water supplied through the pipe 21 is supplied (circulated) from the water tank 33 to the microbubble mixing device 23 through the pipe 19. First, the supply of tap water from the pipe 21 and the supply of PG from the pipe 55 were stopped, and adjustment was made so that an aqueous solution containing microbubbles having a substantially constant concentration could be maintained. The tap water and PG were stopped by closing the open / close valve (not shown) on the pipe 21 path and the flow rate adjusting valve 53 on the pipe 55 path.

  In addition, the microbubble content in the microbubble mixed aqueous solution obtained by the microbubble mixing device (pressure dissolution type device) 23 tends to increase due to the effect that the solute in the aqueous solution becomes a nucleus and generates bubbles. .

  Further, by using the microbubble mixing device (pressure dissolution type device) 23, the dissolved ozone concentration (solubility of ozone in the aqueous solution) (average value) in the aqueous solution containing microbubbles is reduced by the decrease in the liquid temperature. Will increase. Moreover, the total of the ozone concentration in the microbubble in the dissolved ozone concentration and the microbubble mixed aqueous solution increased to 30 ppm or more. The measurement method of the total concentration of dissolved ozone in the microbubble mixed aqueous solution and ozone (gas) in the microbubble was measured using the same method as in the case of ozone water.

  In addition, the content of microbubbles in the aqueous solution mixed with microbubbles tends to increase because the solute in the aqueous solution serves as a nucleus to generate bubbles. The measurement method of the content rate (volume%) of the microbubble in this microbubble mixed aqueous solution was measured using the measurement of volume increase by bubble inclusion.

(3) Bubble mixed aqueous solution supply stage Next, in Experimental Example 8, the bubble mixed aqueous solution supply stage (3) was performed in the same manner as the bubble mixed water supply stage (3) of Example 1 of Experimental Example 1.

  That is, in the bubble-containing aqueous solution supply step (3) of the present experimental example 8, the microbubble-containing aqueous solution generated in the bubble-containing aqueous solution generation step (2) is used below the horizontal lower surface of the cooling surface 27a of the flat cooling member 27. In order to allow the microbubbles 29 to be trapped in the water tank 33 disposed in the tank so that the distal end portion 25a of the bubble-containing aqueous solution supply pipe 25 and the cooling member 27 are in the positional relationship shown in FIG. 2A2. Supplied. The flow rate of the microbubble-mixed aqueous solution into the water tank 33 was adjusted so as to be 5 L / min without being influenced by the change in the concentration of PG.

  Also in this Experimental Example 8, as shown in FIG. 2A2, the flat plate-like cooling member 27 was horizontally installed on the upper portion of the water tank 33 (cooling member cooling surface angle 0 °; downward cooling). In particular, as shown in FIG. 2A2, when the required amount of the microbubble-mixed aqueous solution is supplied to the water tank 33, the cooling surface 27a of the cooling member 27 is substantially below the water surface so that the cooling surface 27a is always below the water surface. The half was placed in the water. The tip 25a of the bubble-containing aqueous solution supply pipe 25 is located below the water tank 33, and expands / contracts in the front / rear direction, or vertically / horizontally, so that the microbubbles 29 can be captured below the horizontal lower surface of the cooling surface 27a. The position was adjusted by bending and stretching.

(4) Ozone Ice Slurry Generation Stage Next, in Experimental Example 8, the ozone ice slurry generation stage (4) was performed in the same manner as the ozone ice generation stage (4) of Example 1 of Experimental Example 1.

  That is, the bubble mixed aqueous solution supply step (3) lowers the liquid temperature of the bubble mixed aqueous solution. Therefore, ethylene glycol is used as the refrigerant from the refrigerant circulation device 37 in the circulation channel 35 inside the cooling member 27 in a state where the microbubbles are captured under the cooling surface 27a of the cooling member 27, and the temperature of the refrigerant is changed to the concentration of PG. Are adjusted to −10 to −15 ° C., about −19 ° C., about −22 ° C., and −25 to −30 ° C. in accordance with 5 to 10% by volume, 15% by volume, 20% by volume and 25% by volume. The cooling surface 27a of the cooling member 27 is also cooled to about −6 to −10 ° C., about −14 ° C., about −17 ° C. and about −20 ° C., and the ice making time is 40 minutes. An ozone ice slurry containing bubbles was generated.

(4a) Exhaust process In Experimental Example 8, the exhaust process (4a) is performed without performing the reuse process during the ozone ice slurry generation stage (4) in the same manner as in Example 1 of Experimental Example 1. The experiment was conducted.

  This Experimental Example 8 is a method for producing an ozone ice slurry generated from a bubble-containing aqueous solution. By making bubble-containing water into an aqueous solution by adding PG, the liquid temperature of the bubble-containing aqueous solution is lowered as described above, and the ozone solubility is reduced. It was confirmed that it increased. As a result, the obtained ozone ice slurry can be refrigerated at a lower temperature. Table 2 below shows controllable refrigeration temperature ranges in the ozone ice slurry obtained by adjusting the addition concentration of PG. The “PG initial concentration” in Table 2 refers to the volume concentration of the added propylene glycol.

  From Table 2, as a result of using PG (melting point: −59 ° C.) as a food additive to make an aqueous solution mixed with bubbles, the concentration of the additive was adjusted. It was confirmed that the refrigeration temperature could be controlled. From this, it was found that the use application can be greatly expanded by making the ozone ozone ice slurry.

  Moreover, it was confirmed that the ozone ice slurry obtained in this Experimental Example 8 also has fluidity and good heat load followability. In addition, the bubble content in the ozone ice slurry obtained in the ozone ice slurry generation stage tends to increase due to the effect of generating bubbles with the solute as a nucleus. Furthermore, the dissolved ozone concentration (average value) in the ozone ice slurry tends to increase with a decrease in temperature, and the ozone gas concentration in the bubbles of the ozone ice slurry also tends to increase as the bubble content increases as described above.

(Experimental example 9: About the example which experimented experimental examples 1-8 by changing the microbubble mixing apparatus 23 into a pressure dissolution type | formula = gas-liquid mixing shearing type)
In this Experimental Example 9, the same conditions (apparatus as in Experimental Examples 1 to 8) except that the gas-liquid mixing shearing type was used by changing the microbubble mixing device 23 used in Experimental Examples 1 to 8 to the pressure dissolution type , Manufacturing conditions), and the same measurement was performed.

  As a result, from the experimental results of each of Experimental Examples 1 to 8 using the pressure dissolution method in the microbubble mixing device 23 and the experimental result of this Experimental Example 9 using the gas-liquid mixed shearing method, the characteristics of the microbubbles are determined. There was no significant difference, and it was confirmed that the same result could be obtained even with the gas-liquid mixed shear method.

  Furthermore, in the gas-liquid mixed shearing method of the ninth embodiment, it is considered that the microbubbles 29 are more easily charged by static electricity generated by the shearing, and therefore can be supplemented below the cooling surface 27a of the cooling member 27 by applying a voltage. It has also been confirmed that it is more effective in increasing the proportion of microbubbles 29 (that is, the bubble content of ice is relatively higher in the gas-liquid mixed shearing method than in the pressure dissolution method). ).

(Experimental example 10: Horizontal lower surface cooling of a flat plate-like cooling member → About bubble-containing ice confectionery with flavor)
In this experimental example 10, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the cooling surface 27a of the flat plate-like cooling member 27 is a horizontal lower surface, and orange juice is easily obtained throughout the year as fruit juice. Using a liquid (fruit juice 100%) (hereinafter simply referred to as fruit juice), a microbubble is produced using a flavored gas (here, citrus flavor gas), and a bubble-containing ice confection with flavor is produced in the juice. did. Here, in this experimental example, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 was 30 L (liter). The amount of fruit juice mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of fruit juice and the liquid level were reduced by ice making). The supply flow rate of the fruit juice mixed with microbubbles into the water tank 33 was 5 L / min. The cooling member 27 is a copper flat plate (8 cm in length, 8 cm in width, 1 cm in thickness) excellent in thermal conductivity whose surface is plated with corrosive electroless nickel, and the cooling surface of the cooling member 27 The area of 27a was 64 cm ² . Moreover, the temperature of the fruit juice supplied from the outside to the microbubble mixing device 23 was room temperature. On the other hand, the temperature of dissolved fruit juice with citrus flavor (hereinafter simply referred to as flavor gas) supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease over time, and during the experiment (40 minutes) It decreased to 0 ° C. or lower.

(1) Bubble mixed fruit production stage In the bubble mixed fruit production stage (1), the flavor gas supplied from the storage unit (gas cylinder) and the fruit juice supplied from the outside (such as a fruit storage tank) through the pipe 21 are microbubbles. It introduce | transduced into the mixing apparatus 23 and produced the microbubble mixed fruit juice. The microbubble mixing device 23 was a pressure dissolution type device.

  Further, in this experimental example, when a necessary amount of microbubble mixed fruit juice is supplied to the water tank 33, the fruit juice supplied from the outside through the pipe 21 is stopped and supplied (circulated) from the water tank 33 through the pipe 19. The flavor gas dissolved fruit juice was introduced into the microbubble mixing device 23 and the production of the microbubble mixed juice was continued.

  Here, the supply amount (volume ratio) of the fruit juice supplied with respect to the flavor gas introduced into the microbubble mixing device 23 is suitably set so that the distribution of the microbubble diameter in the microbubble mixed water is 10 μm to 100 μm. Adjusted.

  In addition, the content of microbubbles in the fruit juice mixed with microbubbles obtained by the microbubble mixing device (pressure dissolution type device) 23 tends to increase due to the effect of generating bubbles with the solute serving as a nucleus.

  Further, by using the microbubble mixing device (pressure dissolution type device) 23, the dissolved flavor concentration in the microbubble mixed fruit juice (the solubility of the flavor gas in the fruit juice) is about the same as in Example 1 of Experimental Example 1. It is estimated that it is possible to adjust to. Moreover, although the flavor gas concentration (average value) in the microbubble in the microbubble mixed fruit juice differs depending on the type of the flavor gas, it is presumed that it can be adjusted to approximately the same level as in Example 1 of Experimental Example 1. .

  Moreover, it is estimated that the content rate (volume%) of the microbubble in microbubble mixed fruit juice can also be adjusted to the same extent as Example 1 of Experimental example 1. FIG.

(2) Bubble mixed fruit supply stage In the bubble mixed fruit supply stage (2), the microbubble mixed fruit juice generated in the bubble mixed fruit generation stage (2) is used as the horizontal lower surface of the cooling surface 27a of the flat cooling member 27. A water tank 33 disposed inside the tank so that the tip 25a of the bubble mixed fruit juice supply pipe 25 and the cooling member 27 are in the positional relationship shown in FIG. 2A2 so that the microbubbles 29 can be captured below. Supplied to. The flow rate of the fruit juice mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

  In the present experimental example, as shown in FIG. 2A2, a flat plate-like cooling member 27 was horizontally installed on the upper portion of the water tank 33 (cooling surface angle of the cooling member: 0 °; cooling downward). In particular, as shown in FIG. 2A2, when the required amount of microbubble mixed fruit juice is supplied to the water tank 33, the flat cooling member 27 is generally arranged so that the cooling surface 27a of the cooling member 27 is always below the liquid level. The lower half was placed in a position where it was immersed in the liquid. The tip 25a of the bubble mixed fruit juice supply pipe 25 is located below the water tank 33, and expands or contracts in the front-rear direction, or vertically and horizontally, so that the microbubbles 29 can be captured below the horizontal lower surface of the cooling surface 27a. The position was adjusted by bending and stretching.

(3) Generation stage of flavored bubble-containing ice In the state where microbubbles are captured under the cooling surface 27a of the cooling member 27 by the bubble mixed water supply stage (2), the circulation flow path 35 inside the cooling member 27 Then, ethylene glycol is used as the refrigerant from the refrigerant circulation device 37, the temperature of the refrigerant is adjusted to -20 to -22 ° C and circulated, and the cooling surface 27a of the cooling member 27 is cooled to about -10 ° C, Ice making time was 40 minutes, and bubble-containing ice with flavor on the cooling surface side was generated.

(3a) Exhaust process In this experimental example, during the generation stage (3) of the bubble-containing ice with flavor, as an exhaust process, the microbubbles 29 in the bubble mixed fruit juice supplied into the water tank 33 are on the liquid surface. The experiment was conducted while exhausting the gasified component from the water tank 33 through the exhaust pipe 41 to the outside of the system.

(4) Ice slurry (ice sherbet) stage In this example, flavor-containing bubble-containing ice 39 generated on the cooling surface 27a of the cooling member 27 obtained in the bubble-containing ice generation stage (3). In the harvesting method (here, a method of circulating a heat medium (ethylene glycol was used as the heat medium) of −20 to −22 ° C. from the refrigerant circulation device 37 to the circulation flow path 35 inside the cooling member 27). The bubble-containing ice 39 with flavors separated in step 1) is scraped off using an ice scraping device (not shown) and slurried (sorbed) (ice slurry stage or ice sherbet stage) An ice confection made of a bubble-containing ice slurry (sorbet) with flavor was produced.

  It was confirmed by Experimental Example 10 that ice confectionery (sorbet) having both a taste of orange and a citrus scent (flavor) (flavor) and a fresh texture that bubbles can blow in the mouth can be generated.

(Experimental example 11: Horizontal bottom cooling of flat cooling member → colored bubble-containing ice)
In this experimental example 11, in the manufacturing method using the ozone ice manufacturing apparatus 10 shown in FIG. 1, the cooling surface 27a of the flat plate-shaped cooling member 27 is a horizontal lower surface, and colorless and transparent tap water is colored. Colored bubble-containing ice (= colored ice) was prepared using a gas (here, a citrus flavor gas and an orange gas). Here, also in the present experimental example 11, the water tank 33 is a sealed water tank having a cubic shape and a lid 33a that can be opened and closed, and the internal volume of the water tank 33 was 30 L (liter). The amount of water mixed with microbubbles stored in the water tank 33 was adjusted to 20 L when the water was full (the amount of water and the liquid level were lowered by ice making). The supply flow rate of the microbubble mixed water into the water tank 33 was 5 L / min. Further, the cooling member 27 is a copper flat plate cooling member (8 cm long, 8 cm wide, 1 cm thick) having excellent thermal conductivity, and the cooling surface 27 a of the cooling member 27 has an area of 64 cm ² . Using. Moreover, the temperature of the tap water supplied from the outside to the microbubble mixing device 23 was about 20 ° C. On the other hand, the temperature of dissolved water (hereinafter simply referred to as colored gas) of citrus flavor gas supplied from the water tank 33 to the microbubble mixing device 23 tends to decrease over time. The inside (40 minutes) had fallen to 2.5-3 degreeC.

(1) Bubble mixed water generation stage In the bubble mixed water generation stage (1), the colored gas supplied from the storage unit (gas cylinder) and the tap water supplied from the outside through the pipe 21 are introduced into the micro bubble mixing apparatus 23. Then, microbubble mixed water was generated. The microbubble mixing device 23 was a pressure dissolution type device.

  Further, in this experimental example 11, when a necessary amount of microbubble mixed water is supplied to the water tank 33, the tap water supplied from the outside through the pipe 21 is stopped and supplied from the water tank 33 through the pipe 19 (circulation). ) The colored gas dissolved water (= colored water) was introduced into the microbubble mixing device 23 and the generation of the microbubble mixed water was continued.

  Here, the supply amount (volume ratio) of tap water supplied to the colored gas introduced into the microbubble mixing device 23 is the distribution of the microbubble diameter in the microbubble mixed water with respect to 100 parts by volume of the colored gas. Was adjusted appropriately to be 10 μm to 100 μm.

  Moreover, the distribution of the microbubble diameter in the microbubble mixed water obtained by the microbubble mixing apparatus (pressure dissolution type apparatus) 23 was in the range of 10 μm to 100 μm, and the average value of the microbubble diameter was 20 μm. The measurement method of the microbubble diameter and its average value was measured using a laser diffraction scattering method.

  In addition, by using the microbubble mixing device (pressure dissolution type device) 23, the concentration of dissolved colored gas (solubility of colored gas in water) (average value) in the water mixed with microbubbles is the example of Experimental Example 1. It is estimated that it can be adjusted to the same degree as 1. Moreover, although the coloring gas component density | concentration (average value) in the microbubble in microbubble mixing water changes with kinds of coloring gas, it is estimated that it can adjust to the substantially same grade as Example 1 of Experimental example 1. FIG. .

  Moreover, the content rate (volume%) of the microbubble in microbubble mixing water was about 10 volume%. The method for measuring the content (volume%) of microbubbles in the water mixed with microbubbles was the same as in Experimental Example 1.

(2) Bubble mixed water supply stage In the bubble mixed water supply stage (2), the microbubble mixed water generated in the bubble mixed water generation stage (2) is used as the horizontal lower surface of the cooling surface 27a of the flat cooling member 27. A water tank 33 arranged inside the tank so that the tip 25a of the bubble mixed water supply pipe 25 and the cooling member 27 are in the positional relationship shown in FIG. 2A2 so that the microbubbles 29 can be captured below. Supplied to. The flow rate of the water mixed with microbubbles into the water tank 33 was adjusted to 5 L / min.

  In this Experimental Example 11, as shown in FIG. 2A2, a flat plate-like cooling member 27 was horizontally installed on the upper portion of the water tank 33 (cooling surface angle of the cooling member: 0 °; downward cooling). In particular, as shown in FIG. 2A2, when the required amount of microbubble mixed water is supplied to the water tank 33, the cooling surface 27a of the cooling member 27 is always below the water surface so that the cooling surface 27a is always below the water surface. The half was placed in the water. The tip 25a of the bubble-mixed water supply pipe 25 is located inside the water tank 33 and extends or contracts in the front-rear direction so that the microbubbles 29 can be trapped below the horizontal lower surface of the cooling surface 27a. The position was adjusted by bending and stretching.

(3) Colored bubble-containing ice generation stage In the state where microbubbles are captured under the cooling surface 27a of the cooling member 27 by the bubble mixed water supply stage (2), the circulation flow path inside the cooling member 27 35, ethylene glycol is used as the refrigerant from the refrigerant circulation device 37, the temperature of the refrigerant is adjusted to -20 to -22 ° C and circulated, and the cooling surface 27a of the cooling member 27 is cooled to about -10 ° C. The ice making time was 40 minutes, and colored bubble-containing ice was generated on the cooling surface side.

(3a) Exhaust process In this experiment example 11, during the generation stage (3) of the colored bubble-containing ice, as an exhaust process, the microbubbles 29 in the bubble-mixed water supplied into the water tank 33 are on the liquid surface. The experiment was conducted while exhausting the gasified component from the water tank 33 through the exhaust pipe 41 to the outside of the system.

  According to the present experimental example 11, the bubble content of the orange bubble-containing ice was 11% by volume, and it was obtained by dissolving the orange gas into a light orange colored water. Bubble-containing ice is a visually effective ice that contains dark orange bubbles in light orange ice, and has a citrus scent (flavor), and when bubbles blow in the mouth It was confirmed that scented ice that can be extracted from the nose can be produced with a new texture.

  Further, an ice slurry was prepared using colored bubble-containing ice.

(4) Ice slurry (ice sherbet) stage In Example 10, colored bubbles generated on the cooling surface 27a of the cooling member 27 obtained in the generation stage (3) of colored bubble-containing ice. The contained ice 39 is subjected to a harvest method (here, a heat medium (-20 ethylene glycol was used as the heat medium) of −20 to −22 ° C. from the refrigerant circulation device 37 to the circulation flow path 35 inside the cooling member 27). The bubble-containing ice 39 that has been peeled off in the circulation method) is scraped off using an ice scraping device (not shown) and slurried (shelved) (ice slurry stage or ice sherbet stage). Performed to produce a colored bubble-containing ice slurry (sorbet).

  It was confirmed that by making ice slurry, ice confectionery (sorbet) having a citrus scent (flavor) with the visual effect of orange and having a new texture that bubbles can be popped in the mouth can be generated.

10 Ozone ice production equipment,
10A ozone ice slurry manufacturing equipment,
11 Ozone raw material department,
13, 17, 19, 21, 55 Piping,
15 Ozone generator,
23 Microbubble mixing device,
25a The tip of the pipe 25,
27 cooling member,
27a Cooling surface (ice-making surface, heat transfer surface) of cooling member,
29 Ozone-containing microbubbles,
29a Ozone-containing bubbles,
31 Ozone water,
33 aquarium,
33a Aquarium lid,
35 circulation channel,
37 Refrigerant circulation device (cooling device),
39 Ozone ice,
39a Ozone ice slurry,
39b ice with only dissolved ozone,
41 exhaust pipe,
43 Supply pipe (pipe),
43a The diameter of the supply pipe (pipe) 43 is increased,
45 water removal means,
45a Peltier element,
45b Hygroscopic agents such as silica gel,
47 power supply,
49 Chlorine removal device,
51 A reservoir of additives that can be slurried into ozone ice,
53 Flow regulator.

Claims (28)

Ozone ice, wherein the gas content (volume ratio) of ice is in the range of 7 to 42% by volume, and the average value of the bubble size (bubble diameter) of the ice is in the range of 70 to 135 μm . The ozone ice according to claim 1, wherein the ice is water obtained by removing chlorine from tap water or groundwater. The gas content (volume ratio) in the ice slurry is in the range of 7 to 42% by volume, and the average value of the bubble size (bubble diameter) in the ice slurry is in the range of 70 to 135 μm. Ozone ice slurry. 4. The ozone ice slurry according to claim 3 , wherein an additive capable of forming an ozone ice slurry is contained in an amount exceeding 0% by volume up to 25% by volume. The ozone ice slurry according to claim 3 , wherein the ozone ice slurry is produced from the ozone ice of claim 1 or 2 using a harvest method. Ozone raw material department,
An ozone generator for generating ozone from the raw material supplied from the ozone raw material section;
A microbubble mixing device that generates microbubble mixed water from ozone-containing gas generated by the ozone generator, ozone water supplied from a water tank and / or water supplied from outside,
(A) The tip of the pipe for supplying the microbubble-mixed water generated by the microbubble-mixing device is in the tank so that microbubbles floating from the microbubble-mixed water can be captured under the cooling surface of the cooling member. And (b) a water tank in which the cooling member is disposed in an upper part or a central part of the tank,
A refrigerant circulation device that circulates a refrigerant in a circulation flow path inside the cooling member to cool at least the cooling surface of the cooling member;
I have a,
An apparatus for producing ozone ice, further comprising a power supply device for applying a voltage to the cooling member . When the cooling member is leveled, the angle of the cooling surface of the cooling member is a reference line (0 °), and the angle formed by the reference line and the cooling surface of the cooling member when the cooling member is tilted The apparatus for producing ozone ice according to claim 6 , wherein the cooling surface angle of the cooling member is a flat cooling member installed in a range of 0 ° to 60 °. The apparatus for producing ozone ice according to claim 7 , wherein the cooling surface angle of the cooling member is a flat plate-shaped cooling member installed in a range of 10 ° to 15 °. The apparatus for producing ozone ice according to any one of claims 6 to 8 , wherein a DC voltage applied to a cooling surface of a cooling member using the power supply device is 100 to 300V. Chlorine removing means is installed on the path for supplying tap water from the outside to the microbubble mixing apparatus, and further on the path for supplying (circulating) ozone water from the water tank to the microbubble mixing apparatus if necessary. The apparatus for producing ozone ice according to any one of claims 6 to 9 , wherein: The microbubble diameter in the microbubble mixed water produced | generated with the said microbubble mixing apparatus is 10-100 micrometers, Moreover, the average value of this microbubble diameter is 20 micrometers, The any one of Claims 6-10 characterized by the above-mentioned. production equipment of ozone ice according to item 1. An exhaust pipe and / or microbubbles in the microbubble-mixed water for evacuating the components gasified by floating the microbubbles in the microbubble-mixed water supplied into the tank to the outside of the system. of but according to any one of claims 6-11, characterized in that further comprising a, a supply pipe for supplying the ozone generator flotation to gasified component onto the liquid surface from the water tank Ozone ice production equipment. And buoyant microbubbles microbubble mixed water is above the liquid surface of the tank in the path for supplying the gasified component to the ozone generator, according to claim 6, characterized by comprising further comprising a moisture removal means - The apparatus for producing ozone ice according to any one of 12 . As the moisture removing means, a portion having an enlarged diameter is provided in the gasified component supply path, and a Peltier element for cooling and dehumidifying the gasified component is installed at the enlarged portion, and / or The apparatus for producing ozone ice according to claim 13 , wherein a moisture absorbent for adsorbing and removing moisture from the gasified component is installed in a supply path of the gasified component. The manufacturing apparatus according to any one of claims 6 to 14 , further comprising a storage section for an additive that can be made into an ozone ice slurry, and a microbubble mixing apparatus from the storage section to water supplied to the mixing apparatus at a predetermined ratio. An ozone ice slurry manufacturing apparatus comprising: a supply path including a flow rate adjusting device for supplying the additive at (volume ratio). The manufacturing apparatus according to any one of claims 6 to 14 , further comprising: (a) an ice scraping device for scraping off the ozone ice peeled off by the harvest method with respect to ozone ice generated on the cooling surface of the cooling member; b) An apparatus for producing an ozone ice slurry, comprising an ice scraping device that can be scraped directly by a scraping method. An ozone generation stage for generating ozone in the ozone generator from the raw material supplied from the ozone raw material section;
Bubble-containing water generation in which the ozone-containing gas generated in the ozone generation stage and the water circulated from the water tank and / or the water supplied from the outside are introduced into the micro-bubble mixing device to generate micro-bubble mixed water Stages,
(A) The tip of the pipe for supplying the microbubble-mixed water generated by the microbubble-mixing device is in the tank so that microbubbles floating from the microbubble-mixed water can be captured under the cooling surface of the cooling member. And (b) a bubble-mixed water supply for supplying microbubble-mixed water generated in the bubble-mixed water generation stage to a water tank in which the cooling member is disposed in the upper or central portion of the tank. Stages,
By supplying and circulating the bubble-mixed water generated by supplying the ozone water in the water tank to the micro-bubble mixing device, the state where the micro-bubbles are captured on the cooling surface side of the cooling member is maintained. However, ozone ice generation is performed to circulate the refrigerant from the refrigerant circulation device through the circulation flow path inside the cooling member, cool at least the cooling surface of the cooling member, and generate ozone ice containing bubbles on the cooling surface side. Stages,
I have a,
A method for producing ozone ice, further comprising a voltage application step of applying a voltage to the cooling member using a power supply device during the ozone ice generation step . The cooling member is a flat cooling member, and when the cooling member is leveled, the angle of the cooling surface of the cooling member is a reference line (0 °), and the cooling member is tilted. the angle between the reference line and the cooling surface of the cooling member (hereinafter, referred to as the cooling surface angle of the cooling member), according to claim 17, characterized in that it is installed in the range of 0 ° to 60 ° Production method of ozone ice. The method for producing ozone ice according to claim 18 , wherein a cooling surface angle of the cooling member is set in a range of 10 ° to 15 °. The method for producing ozone ice according to any one of claims 17 to 19, wherein in the voltage application step, a DC voltage applied to the cooling surface of the cooling member using a power supply device is 100 to 300V. . A path through which ozone water is supplied (circulated) from the water tank to the microbubble mixing apparatus on the path for supplying tap water from the outside to the microbubble mixing apparatus in the bubble mixing water generation stage, if necessary. The method for producing ozone ice according to any one of claims 17 to 20 , further comprising a step of removing chlorine using a chlorine removing apparatus installed on the top. The microbubble diameter in the microbubble mixed water generated by the microbubble mixing apparatus in the bubble mixed water generation stage is 10 to 100 μm, and the average value of the microbubble diameter is 20 μm. The method for producing ozone ice according to any one of claims 17 to 21 . During the ozone ice generation step, an evacuation step for evacuating a component gasified by microbubbles floating in the bubble-mixed water supplied into the water tank from the inside of the water tank and / or the micro 17. microbubbles bubble mixed water is reused process components gasified supplied to the ozone generator flotation to gasified component onto the liquid surface from the water tank, and further comprising - 22. The method for producing ozone ice according to any one of 22 above. During the ozone ice generation stage, using a water removing device installed in a path for supplying microbubbles in the water mixed with microbubbles floated on the liquid surface of the water tank and gasified components in the ozone generator, The method for producing ozone ice according to any one of claims 17 to 23 , further comprising a step of removing moisture from the gasified component. As the moisture removal means, (a) a Peltier element for providing a location where the diameter of the microbubble is expanded in the gasification component supply path, and cooling and dehumidifying the gasified component at the expanded location, and / or, according to claim 24, characterized in that installed the hygroscopic agent for adsorbing and removing water from the component (b) the microbubbles is the gasification in the supply path of the component gasified Manufacturing method of ozone ice. 26. In the production method according to claim 17 to 25 , during the bubble-mixed water generation step, further through a supply path provided with a flow rate adjusting device from a storage part of an additive that can be made into ozone ice slurry to a micro-bubble mix device. A method for producing an ozone ice slurry, comprising a step of supplying the additive at a predetermined ratio (volume ratio) to a flow rate of water supplied to the mixing device. The manufacturing method according to claim 17 to 25 , wherein the ozone ice generated on the cooling surface of the cooling member is (a) scraped off the ozone ice peeled off by the harvest method using an ice cutting device. A method for producing an ozone ice slurry, comprising: a step of slurrying, or (b) a step of scraping and slurrying directly using an ice scraping device by a scraping method. Use of the manufacturing apparatus according to any one of claims 6 to 16 and use of the manufacturing method according to any one of claims 17 to 27 to produce bubble-containing ice formed into ice or an ice making slurry. or a ice slurry ranges bubble content of ice or ice slurry (volume ratio) is 7-42% by volume, average bubble size of the ice or ice-slurry (cell diameter) is, Ice or ice slurry characterized by being in the range of 70-135 μm .