JP6463342B2 - Viscous bubble liquid production apparatus and viscous bubble liquid production method using the same - Google Patents

Description

  The present invention relates to a viscous bubble liquid capable of holding bubbles for a long time, a manufacturing method thereof, a manufacturing apparatus thereof, and a storage method thereof.

  In recent years, research on the use of bubbles has been advanced in various fields such as ultrasonic echo inspection technology.

  For example, Non-Patent Document 1 shows that bubbles are a good reflection source of ultrasonic waves and are suitable as an ultrasonic contrast agent.

  Non-Patent Document 1 includes the following points as the reason. (1) Ultrasonic waves are reflected at boundaries where there is a difference in acoustic impedance. (2) The degree of reflection and transmission is determined by the difference in acoustic impedance. (3) A material having an acoustic impedance different from that of water present in a living tissue or a living body is a gas. (4) The amount of ultrasonic reflection is proportional to the sixth power of the bubble diameter.

  In addition, from the description of (4) above, it can be seen that a material containing large bubbles is suitable for examining a lumen in a living body.

  Patent Document 1 discloses that in an ultrasonic examination of a digestive organ, an oral ultrasonic contrast agent contains microbubbles as an ultrasonic reflector in order to increase the ultrasonic echo intensity.

  The above-mentioned oral ultrasonic contrast agent contains a liquid having high ultrasonic permeability such as water and castor oil, and a composition composed of alginate or the like for adjusting the viscosity of the contrast agent in the digestive tract.

  Alginates have the property that they can increase the viscosity of the liquid in the digestive tract under an acidic environment or a polyvalent ion acidic environment. For this reason, by adding the above composition to the liquid, the oral ultrasound contrast agent can increase the viscosity to the extent that it stays in the digestive tract while being low in viscosity and easy to drink during oral injection. Can be obtained.

  According to Patent Document 1, the above-mentioned oral ultrasonic contrast agent is contained in a suitable container and stirred or shaken by hand or a predetermined instrument, or microbubbles are removed using a homogenization pump such as a homogenizer. By forming it, the above-mentioned oral ultrasonic contrast agent contains microbubbles.

  Patent Document 1 discloses that when microbubbles are formed, a surfactant is included in the liquid to promote the formation of microbubbles, and a film is formed around the microbubbles to form microbubbles. It is disclosed that it can be protected.

  In addition to the detection of abnormalities in the human body in medical ultrasonic diagnostics, the ultrasonic echo inspection technology is a technique for noninvasively visualizing parts that cannot be seen with the naked eye, such as detecting abnormalities in piping in nondestructive inspection, for example. Widely used in medical and industrial fields.

Japanese Patent Publication “JP 10-306042 A” (published November 17, 1998)

Koji Tsuchiya, “Development of Ultrasound Contrast Microbubbles for Early Medical Diagnosis”, Proceedings of the 12th Microbubble Application Technology Lecture, June 28, 2013, p16-p31 Hirai Seiko, Makoto Kamura, “High-concentration microbubble generator and its application”, raw material, March 2008, p44-47

  However, as shown in Patent Document 1, the time during which bubbles are present in a bubble liquid containing bubbles such as a contrast medium is usually very short as 1 minute or less.

  In addition, Patent Document 1 actually increases the viscosity of an oral ultrasonic contrast agent in a digestive organ after oral injection, and retains the oral ultrasonic contrast agent in the digestive organ to perform ultrasonic diagnostic imaging. It is something to execute.

  However, as described in Patent Document 1, even when the viscosity of an oral ultrasonic contrast agent containing bubbles is experimentally increased in an acidic environment or a polyvalent ion acidic environment, the lifetime of the bubbles is reduced so much. It cannot be extended. Patent Document 1 describes that when a 0.5% aqueous sodium alginate solution containing bubbles is used as an oral ultrasonic contrast agent, the lifetime of microbubbles can be extended to about 5 minutes to about 10 minutes. ing.

  However, with such an extension of the lifetime of bubbles, even if bubbles are included in the ultrasonic contrast agent, the bubbles disappear at the stage of preparation for ultrasonic examination.

  In addition, when the produced oral ultrasonic contrast agent is not used, it is necessary to store it, but there is no method for stably containing the bubbles in the oral ultrasonic contrast agent for a long time. For this reason, since it is necessary to manufacture an oral ultrasonic contrast agent each time at the time of ultrasonic inspection, the inspection work becomes complicated.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a viscous bubble liquid capable of holding bubbles for a long time, a manufacturing method thereof, a manufacturing apparatus thereof, and a storage method thereof.

  The inventors of the present application have made extensive studies in order to provide a viscous bubble liquid capable of holding bubbles for a long time.

  As a result, the inventors of the present application can reduce the lifetime of bubbles by dispersing bubbles formed by mixing bubbles in warm water containing a surfactant and a gelling agent in an aqueous solution containing a thickener. I found out that it can be long.

  In addition, the inventors of the present application have a viscous bubble liquid in which a foam in which a gas is encapsulated in a film containing a surfactant and a gelling agent is dispersed in an aqueous solution containing a thickener. It has been found that the bubbles can be held for a long time, and the present invention has been completed.

  Further, the inventors of the present application have found that by storing the viscous bubble liquid under pressure, the viscous bubble liquid can be stored while stably containing the bubbles in the viscous bubble liquid for a long time. It was.

  That is, in the viscous bubble liquid according to one aspect of the present invention, a foam in which a gas is included in a film containing a surfactant and a gelling agent is dispersed as bubbles in a viscous liquid made of an aqueous solution containing a thickener. Has been.

  Moreover, the method for producing a viscous bubble liquid according to one aspect of the present invention is a method in which a foam formed by introducing a gas into warm water containing a surfactant and a gelling agent is converted into a viscosity comprising an aqueous solution containing a thickener. Disperse as bubbles in the liquid.

  Moreover, the viscous bubble liquid manufacturing apparatus according to one aspect of the present invention is a viscous bubble liquid manufacturing apparatus used in the above-described viscous bubble liquid manufacturing method, and contains hot water containing a surfactant and a gelling agent. A first container; a second container containing a viscous liquid composed of an aqueous solution containing a thickener; a gas introducer for introducing gas into the warm water in the first container; the first container; A foam moving unit that connects the two containers and moves the foam formed on the liquid surface of the warm water to the second container by introducing a gas into the warm water in the first container. ing.

  Moreover, the storage method of the viscous bubble liquid concerning 1 aspect of this invention stores the said viscous bubble liquid under pressure.

  According to one embodiment of the present invention, it is possible to provide a viscous bubble liquid capable of holding bubbles for a long time, a manufacturing method thereof, a manufacturing apparatus thereof, and a storage method thereof.

It is sectional drawing which shows typically an example of the viscous bubble liquid manufacturing apparatus concerning Embodiment 1 of this invention. It is sectional drawing which shows typically an example of the viscous bubble liquid manufacturing apparatus concerning Embodiment 2 of this invention. (A)-(c) is sectional drawing which shows the manufacturing method of the viscous bubble liquid concerning one Embodiment of this invention in order of a process. It is sectional drawing which shows the apparatus used for the measurement of the physical property of the bubble in the viscous bubble liquid obtained in the Example of this invention. (A) is a figure which shows the optical micrograph of the viscous bubble liquid immediately after manufacture in the Example of this invention, (b) is 3 days after manufacture when manufacturing it refrigerated at 5 degreeC after manufacture. In the optical micrograph of the viscous bubble liquid, it is a diagram showing a circle for measuring the bubble diameter superimposed on the edge of the bubble. It is a graph which shows volume distribution of the viscous bubble liquid immediately after manufacture in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid after progress for three days from manufacture in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid after seven days progress from manufacture in the Example of this invention. It is a graph which shows the volume distribution of the viscous bubble liquid after progress for 35 days from manufacture in the Example of this invention. It is a graph which shows transition of the void ratio of the viscous bubble liquid in the Example of this invention. It is a graph which shows bubble diameter distribution of the viscous bubble liquid after progress for three days from manufacture in the Example of this invention. It is a graph which shows the raise speed | velocity | rate and moving time of the normal bubble of diameter 1mm in each liquid from which a viscosity differs. It is a figure which shows the contrast image which used the viscous bubble liquid obtained in the Example of this invention as a contrast agent. It is a graph which shows transition of the void ratio of the viscous bubble liquid in the case where the internal pressure is applied to the pressurized storage container and the case where it is not applied in Embodiment 3 of the present invention. It is a graph which shows the decreasing rate of the void rate of the viscous bubble liquid after seven days progress from manufacture when the internal pressure of a pressurized storage container is changed in Embodiment 3 of this invention. It is a graph which shows the void ratio of each viscous bubble liquid obtained by changing the temperature of the aqueous solution containing surfactant and a gelatinizer in Embodiment 4 of this invention. It is a graph which shows transition of the void ratio of the viscous bubble liquid in the viscous bubble liquid which contains hydrogen gas as a bubble concerning Embodiment 5 of this invention.

  Hereinafter, an embodiment of the present invention (hereinafter simply referred to as “form”) will be described in detail.

(Viscous bubble liquid and method for producing viscous bubble liquid)
The viscous bubble liquid according to this embodiment is a bubble liquid in which a foam in which a gas is included in a film containing a surfactant and a gelling agent is dispersed as bubbles in a viscous liquid made of an aqueous solution containing a thickener. is there.

  Moreover, the manufacturing method of the viscous bubble liquid concerning this form is a viscous liquid which consists of the foam formed by introduce | transducing gas into the warm water containing surfactant and a gelatinizer in the aqueous solution containing a thickener. This is a method of dispersing as bubbles.

  The surfactant is not particularly limited, and various known surfactants having a foaming action can be used. For example, when the viscous bubble liquid is used for a medical contrast medium (oral contrast medium), examples of the surfactant include lecithin (for example, extracted from plant lecithin extracted from soybeans, rapeseed, and egg yolk). A surfactant mainly used for food additives is used as an emulsifier, such as egg yolk lecithin), glycerin fatty acid ester, sucrose fatty acid ester, stearoyl calcium lactate, sorbitan fatty acid ester, propylene glycol fatty acid ester and the like. The surfactant may be used alone or in combination of two or more.

  The gelling agent is not particularly limited as long as it dissolves or disperses in water and gels water containing the gelling agent at room temperature. As the gelling agent, a known gelling agent can be used. Examples of the gelling agent include gelatin, carrageenan, locust bean gum and the like.

  These gelling agents may be used alone or in combination of two or more. As an example of the gelling agent formed by mixing two or more of these gelling agents, for example, “Gel-up WM” (trade name, manufactured by San-Eigen FFI Co., Ltd., composition: carrageenan 28% by weight, locust bean gum 17 4%, calcium lactate (stabilizer) 6.6%, food material 48%) and the like.

  As the gelling agent, alginates and calcium can be used. Gelling occurs when an alginate and calcium ions are cross-linked. Then, it can use as a gelatinizer by using together alginate and calcium compounds, such as a calcium chloride and calcium carbonate. Moreover, as calcium used for the said gelatinizer, the foodstuff containing calcium may be sufficient.

  As said alginate, sodium alginate etc. can be used, for example. Moreover, as said alginate, "Kimika argin" (brand name) by Kimika Co., Ltd. can be used, for example.

  The thickener is not particularly limited as long as it dissolves in water and causes viscosity at room temperature.

  However, when the above viscous bubble liquid is used for a human body such as a medical contrast medium, it is necessary to use a thickener that is safe for the human body even if it is drunk. On the other hand, when the viscous bubble liquid is used for industrial purposes such as a contrast agent in non-destructive inspection of piping, it may be anything as long as it does not damage an object to be used such as piping.

  As the thickener, a known thickener can be used. Examples of the thickener include thickening polysaccharides such as CMC (carboxymethylcellulose) and “Thoromi Up Perfect” (trade name, manufactured by Nisshin Oilio).

  The said gas is not specifically limited, According to a use etc., it can select suitably. For example, when the viscous bubble liquid is used as a medical contrast agent, a gas that is harmless to the human body is used as the gas. Examples of such a gas include air, oxygen, nitrogen, hydrogen, carbon dioxide and the like.

  According to this embodiment, the gas is encapsulated in the coating film containing the surfactant and the gelling agent by introducing the gas into the warm water containing the surfactant and the gelling agent and mixing the bubbles into the warm water. A foam is formed.

  As a result of intensive studies by the inventors of the present application, the production of the viscous bubble liquid having a long bubble life intended in this embodiment requires both a surfactant and a gelling agent to form the foam.

  From this, the foam constituting the bubbles in the viscous bubble liquid contains a gas, like a normal soap bubble, and is arranged with a hydrophobic group on the inner side (gas side) and a hydrophilic group on the outer side. It is considered that the surfactant has a structure in which the surfactant is doubly arranged, and the gelling agent plays a role of linking the doubly arranged surfactant.

  In this embodiment, the concentration of the surfactant in the warm water may be appropriately set so as to obtain a desired foam according to the type of the surfactant to be used, and is not particularly limited. For example, it is in the range of 0.1 to several weight percent.

  Further, the concentration of the gelling agent in the warm water may be set as appropriate so as to obtain a desired foam according to the type of the gelling agent to be used, and is not particularly limited. In the range of 0.2 to 2% by weight.

  As the surfactant and the gelling agent, for example, a surfactant (emulsifier) and a gelling agent that are commercially available as food supplements can be used. Can be used within a range of aliquots.

  Moreover, what is necessary is just to set suitably the mixture ratio of the said surfactant and a gelatinizer so that a desired foam may be obtained according to the kind of surfactant and gelatinizer to be used. It can be appropriately changed within the range.

  Therefore, the blending ratio of the surfactant and the gelling agent is not particularly limited. For example, by using the surfactant and the gelling agent in a ratio of 1: 1, the examples described later can be used. As shown, it is possible to form a foam capable of obtaining long-lived bubbles.

  Moreover, the said warm water should just be able to disperse | distribute or dissolve the said surfactant and a gelatinizer uniformly.

  Tap water, potable water, etc. can be used for the warm water, and it is not always necessary to use pure water or ion-exchanged water. In other words, the hot water may be water as its main component.

  The temperature of the warm water is not particularly limited as long as the surfactant and gelling agent can be uniformly dispersed or dissolved.

  Further, the time from introduction of the surfactant and gelling agent into the warm water until gas introduction is not particularly limited, and the surfactant and gelling agent are uniformly dispersed or dissolved in the warm water. It only has to be made.

  However, since the meaning of sterilization and the property that the surfactant and the gelling agent are difficult to dissolve or disperse in water, the temperature of the warm water is, for example, about 85 ° C. (especially 85 ° C. from the viewpoint of sterilization). It is desirable to set the temperature to about 85 ° C. for several minutes after the surfactant and the gelling agent are added to the warm water.

  The gas is introduced into warm water containing the surfactant and the gelling agent in a state where the surfactant and the gelling agent are uniformly dissolved or dispersed in the warm water.

  For introducing the gas into the hot water, a bubble generator such as a porous bubble generator or a swirling bubble generator can be used as the gas introducer.

  Specifically, the foam is formed by generating bubbles with a bubble generator in a liquid in which a surfactant and a gelling agent are uniformly dissolved or dispersed in warm water.

  When gas is introduced into the liquid in which the surfactant and the gelling agent are uniformly dispersed in this manner to generate bubbles, the gas is contained inside the coating formed by the surfactant and the gelling agent. A state of foam is formed. And the formed foam accumulates on the liquid level of the liquid.

  The viscous bubble liquid concerning this form can be obtained by disperse | distributing this foam as a bubble in the viscous liquid which consists of the aqueous solution containing a thickener.

  According to this embodiment, by dispersing the foam in the viscous liquid, it is possible to retain the bubbles made of the foam, for example, in a space to be observed for a certain period of time.

  The lifetime of submillimeter class bubbles in an aqueous solution generally depends on the viscosity of the aqueous solution. In the aqueous solution having a high viscosity, the bubble life becomes long. However, if the viscosity is excessively increased, it becomes difficult to introduce the viscous bubble liquid into the introduction target to be introduced.

  For example, when the viscous bubble liquid is used as a contrast agent for confirming the swallowing function in the human body, it is important whether or not the viscous bubble liquid has a viscosity that allows it to stay and swallow. If the viscosity of the viscous bubble liquid is made too high, the residence time of the viscous bubble liquid in the human body can be increased, but there is a possibility that it will likely suffocate. For this reason, when using the said viscous bubble liquid as a medical contrast agent, it is necessary to adjust to the viscosity suitable for a medical contrast agent.

  For example, when a viscous bubble liquid is used as a medical contrast agent for inspection in the oral cavity, it must usually be kept at a viscosity of about several tens to several hundreds mPa · s.

  Further, when the viscous bubble liquid is used as, for example, a contrast agent for nondestructive inspection of piping, the inner diameter of the piping and the configuration state of the piping (for example, whether the piping is connected to a pump or the like, whether the piping is closed) Depending on the number and angle of bending, etc., the conditions for flowing at an appropriate speed are different.

Therefore, even if the case where the above viscous bubble liquid is used as a contrast agent, for example,
Optimization is required for each system to be observed.

For this reason, the viscosity of the aqueous solution is not particularly limited, but is, for example, within a range of 1 × 10 ² to 1 × 10 ⁶ mPa · s at room temperature (for example, a viscosity equivalent to sauces, yogurt, mayonnaise, etc. ).

  In addition, the density | concentration of the thickener in the said aqueous solution is suitably set so that the viscosity of the said aqueous solution may turn into a desired viscosity, and is not specifically limited.

  Moreover, the mixing conditions such as time and temperature for mixing the foam in the aqueous solution are not particularly limited, and may be set as appropriate so that the foam can be uniformly dispersed in the aqueous solution.

  The foam may be mixed with the aqueous solution at normal temperature and normal pressure. If necessary, the viscosity of the aqueous solution is heated and stirred and mixed in order to uniformly disperse the foam in the aqueous solution. It may be adjusted to mix.

  Moreover, the said aqueous solution may contain the well-known additive etc. which are used as a food supplement etc. as needed.

(Viscous bubble liquid production equipment)
Embodiment 1
Next, as an example of a viscous bubble liquid production apparatus according to the present embodiment, a viscous bubble liquid production apparatus using a porous fine bubble generator will be described with reference to FIG.

  FIG. 1 is a cross-sectional view schematically showing an example of the viscous bubble liquid production apparatus 1 according to the present embodiment.

  The viscous bubble liquid manufacturing apparatus 1 shown in FIG. 1 includes a foam forming unit 10, a foam moving unit 20, and a foam mixing unit 30.

  The foam forming unit 10 in the viscous bubble liquid production apparatus 1 shown in FIG. 1 includes a heating / stirring device 11 (first container), a compressor 12, a porous fine bubble generator 13 (gas introducing device), and a stirring device. A child 14, a pressure gauge 15, and a relief valve 16 are provided.

  The heating / stirring device 11 is composed of a sealable container having a heating function and a stirring function such as an electromagnetic stirrer. The heating / stirring device 11 stirs the material supplied into the heating / stirring device 11 by rotating the stirrer 14 disposed in the heating / stirring device 11 with an electromagnetic stirrer or the like.

  The heating / stirring device 11 includes a container portion 11a that is a main body of the heating / stirring device, and a lid portion 11b that can seal the container portion 11a.

  Inside the heating / stirring device 11, a porous microbubble generator 13 connected to a compressor 12 disposed outside the heating / stirring device 11 is disposed as a microbubble generator. The porous fine bubble generator 13 includes a porous material (not shown) inside, and introduces a gas into the liquid in the container portion 11a through the porous material, so that the liquid in the container portion 11a Generate and mix fine bubbles.

  For this reason, the porous microbubble generator 13 is provided so as to be positioned below the liquid level of the liquid supplied into the container portion 11a.

  The material and pore diameter of the porous material may be appropriately selected so that bubbles having a desired size can be generated, and are not particularly limited.

  In addition, the lid 11b of the heating / stirring device 11 has a pressure gauge 15 for measuring the pressure in the heating / stirring device 11 and the pressure in the heating / stirring device 11 is equal to or higher than a set pressure (threshold). A relief valve 16 that sometimes discharges excess gas is attached.

  The pressure inside the heating / stirring device 11 is controlled by a pressure control mechanism including a compressor 12, a pressure gauge 15, and a relief valve 16.

  The foam mixing unit 30 includes a heating device 31 (second container) and a stirrer 32.

  The heating device 31 is composed of a sealable container having a heating function. The heating device 31 includes a container portion 31a that is a heating device main body, and a lid portion 31b that is provided so as to be able to seal the container portion 31a.

  In the example illustrated in FIG. 1, the heating device 31 is illustrated as an example in which the liquid 43 in the heating device 31 is stirred by the stirrer 32 attached to the lid portion 31 b.

  However, the viscous bubble liquid manufacturing apparatus 1 according to the present embodiment is not limited to this, and in the same manner as the foam forming unit 10, instead of the heating device 31, a heating / stirring function having a heating function and a stirring function is provided. An apparatus may be used. In this case, similarly to the foam forming unit 10, the liquid 43 in the heating / stirring device can be stirred by using a stirring bar.

  The foam moving unit 20 includes a connecting tube 21 that connects the foam forming unit 10 and the foam mixing unit 30, and a heat insulating material 22 that covers the connecting tube 21.

  The foam 41 formed by the foam forming unit 10 and containing the introduced gas inside accumulates on the liquid level of the liquid 42 in the heating / stirring device 11. The foam moving unit 20 moves the foam 41 on the liquid surface of the liquid 42 from the foam forming unit 10 to the foam mixing unit 30 through the connecting pipe 21 that is prevented from being cooled by the heat insulating material 22 or the like.

  For this reason, the opening 21 a of the connecting pipe 21 in the foam forming unit 10 is provided at a position higher than the liquid level of the liquid 42 in the heating / stirring device 11.

  In addition, the connecting tube 21 is provided to be inclined so as to descend from the foam forming unit 10 toward the foam mixing unit 30 in order to smoothly move the foam 41 from the foam forming unit 10 to the foam mixing unit 30. .

  For this reason, the opening part 21b of the connection pipe 21 in the foam mixing part 30 is higher than the liquid level of the liquid 43 in the heating device 31, and is lower than the opening part 21a of the connection pipe 21 in the foam forming part 10. Is formed.

(Method for producing viscous bubble liquid using viscous bubble liquid production apparatus)
Next, an example of a method for producing a viscous bubble liquid (viscous bubble water) using the viscous bubble liquid production apparatus 1 shown in FIG. 1 will be described.

  First, water is charged into the heating / stirring device 11 in the foam forming unit 10 and heated to 85 ° C., and then a surfactant and a gelling agent are added to the obtained warm water. Next, the stirrer 14 stirs until the surfactant and the gelling agent are uniformly dispersed or dissolved in the warm water.

  On the other hand, water is charged into the heating device 31 in the foam mixing unit 30, and the thickening polysaccharide is added and stirred to dissolve. At this time, if necessary, the water in the heating device 31 may be heated in order to dissolve the thickening polysaccharide in water. When the above viscous bubble liquid is used for an oral contrast agent, for example, the viscosity of the liquid 43 (viscous aqueous solution) in the heating device 31 is finally adjusted to be several tens to several hundreds mPa · s at room temperature. It is desirable.

  The gas is then passed from the compressor 12 to the porous microbubble generator 13. As a result, as described above, the gas is introduced from the porous microbubble generator 13 into the liquid 42 in the heating / stirring device 11 obtained by dispersing or dissolving the surfactant and the gelling agent in warm water. And fine bubbles are generated.

  The optimum pressure at this time varies depending on the material of the porous material in the porous fine bubble generator 13, but when a resin porous material is used, a pressure of about 0.2 MPa is required.

  As an example, when “Foamest” (registered trademark, micro-nano bubble generator manufactured by NAC Co., Ltd.) is used for the porous microbubble generator 13, the porous material includes a monolaton film and The so-called polymer film is used. In the monolaton film, a porous part having a width of 4 to 10 μm is processed into a film having a thickness of 50 to 200 μm at intervals of 20 to 30 μm, and pores (voids having a diameter of 5 to 20 nm are formed in the porous part. ) Is provided. When a compressed gas of 0.03 to 0.3 MPa is added to the monolaton film, the gas passes through the voids of the porous portion, and micro-nano bubbles are generated.

  However, the porous fine bubble generator 13 is not limited to this. For example, a porous fine bubble generator 13 using shirasu porous glass can be used as the porous material. Examples of the porous material using Shirasu porous glass include Shirasu porous glass membrane (SPG membrane, pore size variation 0.05 to 50 μm) manufactured by SPG Techno Co., Ltd.

  As described above, when bubbles are generated in a state where the surfactant and the gelling agent are uniformly dispersed or dissolved in the liquid 42, the gas is contained inside the coating formed by the surfactant and the gelling agent. A foam 41 in a state is formed and accumulates on the liquid surface of the liquid 42 as shown in FIG.

  The foam 41 is transferred to the heating device 31 in the foam mixing unit 30 via the foam moving unit 20 in which cooling is prevented by a heat insulating material or the like.

  Thereby, the said foam 41 is disperse | distributed in the liquid 43 in the heating apparatus 31 which adjusted the viscosity previously with the thickening polysaccharide. Thereby, a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate can be generated.

[Embodiment 2]
Next, as an example of a viscous bubble liquid production apparatus according to the present embodiment, a viscous bubble liquid production apparatus using a swirling flow type fine bubble generator (shear flow type fine bubble generator) will be described with reference to FIG. Will be described below. In the following, for convenience of explanation, components having the same functions as those in FIG. 1 are denoted by the same reference numerals, and description thereof is omitted.

  FIG. 2 is a cross-sectional view schematically showing another example of the viscous bubble liquid manufacturing apparatus 1 according to the present embodiment.

  The viscous bubble liquid manufacturing apparatus 1 illustrated in FIG. 2 includes a foam forming unit 10, a foam moving unit 20, and a foam mixing unit 30, similar to the viscous bubble liquid manufacturing apparatus 1 illustrated in FIG. 1.

  However, the foam forming unit 10 in the viscous bubble liquid production apparatus 1 shown in FIG. 2 includes a heating device 51 (first container), a water flow pump 52, a swirling flow type fine bubble generator 53 (gas introduction device), A pressure gauge 15 and a relief valve 16 are provided.

  The heating device 51 is composed of a sealable container having a heating function. The heating device 51 includes a container portion 51a that is a heating device main body, and a lid portion 51b that is provided so as to be able to seal the container portion 51a.

  A water flow pump 52 and a swirl type fine bubble generator 53 are attached to the heating device 51.

  The heating device 51 circulates the liquid 42 in the heating device 51 with the water flow pump 52 and stirs it.

  The swirling flow type fine bubble generator 53 includes an intake port 53 a and a liquid suction port 53 b, and is circulated by a water flow pump 52 and a gas that is sucked into the swirl flow type fine bubble generator 53 from the intake port 53 a. Thus, the liquid 42 taken in from the liquid suction port 53b is mixed to generate a gas-liquid mixed solution. In the swirling flow type fine bubble generator 53, the gas-liquid mixture is spirally introduced into a cylindrical cylinder, and the gas is refined by centrifugal force acting on the gas-liquid. The refined gas-liquid mixture is discharged into the liquid 42 in the heating device 51 from the discharge port 53c.

  The lid 51b of the heating device 51 discharges surplus gas when the pressure gauge 15 for measuring the pressure in the heating device 51 and the pressure in the heating device 51 become a set pressure (threshold) or more. A relief valve 16 is attached.

  The pressure inside the heating device 51 is controlled by a pressure control mechanism including a water flow pump 52, a pressure gauge 15, and a relief valve 16.

  In addition, the structure of the foam mixing part 30 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 2 is the same as the structure of the foam moving part 20 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG. Moreover, the structure of the foam moving part 20 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG. 2 is the same as the structure of the foam moving part 20 in the viscous bubble liquid manufacturing apparatus 1 shown in FIG.

  Therefore, regarding the foam mixing unit 30 and the foam moving unit 20, in the description of FIG. 1, the heating / stirring device 11 is replaced with the heating device 51, and the description thereof is omitted here.

(Method for producing viscous bubble liquid using viscous bubble liquid production apparatus)
Next, an example of a method for producing a viscous bubble liquid using the viscous bubble liquid production apparatus 1 shown in FIG. 2 will be described.

  First, water is charged into the heating device 51 in the foam forming unit 10 and heated to 85 ° C. Then, a surfactant and a gelling agent are added to the obtained hot water. Next, the liquid 42 in the heating device 51 is circulated and stirred by the water flow pump 52, whereby the surfactant and the gelling agent are uniformly dispersed or dissolved in the warm water.

  Next, a gas-liquid mixture is generated from the gas self-primingly introduced into the swirling flow type fine bubble generator 53 and the circulating liquid 42, and this is spiraled into the swirling flow type fine bubble generator 53. The gas is refined by being introduced into the shape and discharged into the liquid 42 in the heating device 51 from the discharge port 53c.

  In this way, when bubbles are generated in a state where the surfactant and the gelling agent are uniformly dispersed in the liquid 42, the gas is contained inside the coating formed by the surfactant and the gelling agent. Foam 41 is formed and accumulates on the surface of liquid 42 as shown in FIG.

  In this example also, on the other hand, water is charged into the heating device 31 in the foam mixing unit 30, and the thickening polysaccharide is added and stirred to dissolve. At this time, if necessary, the water in the heating device 31 may be heated in order to dissolve the thickening polysaccharide in water. When the above viscous bubble liquid is used for an oral contrast agent, for example, the viscosity of the liquid 43 (viscous aqueous solution) in the heating device 31 is finally adjusted to be several tens to several hundreds mPa · s at room temperature. It is desirable.

  Next, the foam 41 accumulated on the liquid surface of the liquid 42 is transferred to the heating device 31 in the foam mixing unit 30 via the foam moving unit 20 in which cooling is prevented by a heat insulating material or the like.

  Thereby, also in this example, the said foam 41 is disperse | distributed in the liquid 43 in the heating apparatus 31 which adjusted the viscosity previously with the thickening polysaccharide. Thereby, a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate can be generated.

(Modification)
Next, an example of a method for producing a viscous bubble liquid using alginate will be described.

  When, for example, calcium chloride or calcium carbonate is used as the gelling agent and alginates and calcium for gelling the alginate, the liquid 42 is prepared as follows.

  First, water is charged in the heating / stirring device 11 or the heating device 51 in the foam forming unit 10 and heated to 85 ° C., and then the surfactant and the alginate are added to the obtained warm water and sufficiently stirred. .

  Thereafter, calcium chloride or calcium carbonate is added to the heating / stirring device 11 or the heating device 51, and after sufficiently stirring again, the fine bubbles are generated by the porous fine bubble generator 13 or the swirl flow fine bubble generator 53. Is generated. Thereby, also in this example, the foam 41 in a state containing gas is formed inside the film formed of the surfactant and the gelling agent, and the liquid 42 in the heating / stirring device 11 or the heating device 51 is formed. Accumulate on the surface.

  Then, also in this example, the said foam 41 is disperse | distributed in the liquid 43 in the heating apparatus 31 which adjusted the viscosity previously with the thickening polysaccharide. Thereby, a viscous bubble liquid having a high bubble concentration and a slow bubble extinction rate can be generated.

〔Example〕
Hereinafter, the viscous bubble liquid according to the first and second embodiments and the manufacturing method thereof will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

  Below, the result of having produced viscous bubble liquid on a small scale simply (production | generation) and evaluating the performance of the obtained viscous bubble liquid is shown.

  (A)-(c) of FIG. 3 is sectional drawing which shows the manufacturing method of a viscous bubble liquid in order of a process.

  First, as shown in FIG. 3A, an electromagnetic cooking pan 62 containing 500 cc of tap water as water is placed on an electromagnetic heater 61, and the temperature is measured by a thermometer 63. The water in the cooking pan 62 was heated to 85 ° C.

  Next, while stirring the water (warm water) in the electromagnetic cooking pan 62 with the stirrer 64, 0.5 wt% lecithin is added to the water as a surfactant in the electromagnetic cooking pan 62. I put it in little by little.

  Next, while stirring the mixed solution in the electromagnetic cooking pan 62 with the stirrer 64, 0.5% by weight of “gel up WM” is added to the water as a gelling agent in the electromagnetic cooking pan 62. Was added little by little to obtain an aqueous solution 81 as a liquid (liquid 42) containing the surfactant and the gelling agent.

  Next, as shown in FIG. 3B, the obtained aqueous solution 81 is transferred to a beaker 65 having an appropriate size (for example, a 1 L beaker), and a stirrer 66 is placed in the beaker 65 and stirred with a stirrer 67. While cooling naturally.

  Thereafter, when the temperature of the aqueous solution 81 in the beaker 65 fell below 65 ° C., bubbles were generated by the bubble generating device 69 connected to the compressor 68. As the bubble generating device 69, a column-type “Foamest” (registered trademark), which is a porous micro-nano bubble generating device manufactured by Nac Co., Ltd., was used.

  As a result, a foam part formed by accumulating a plurality of foams 41 was formed on the liquid surface of the aqueous solution 81 in the beaker 65.

  Next, all the foam 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 was collected in another beaker 71 as shown in FIG.

  On the other hand, “Toromi Up Perfect”, which is a thickening polysaccharide “Thorimi Up Perfect” as a liquid 43 (viscous liquid) in another beaker 72 at a concentration of 1% by weight in water (tap water). A thickening liquid 82 consisting of an aqueous solution was prepared. The viscosity of the thickening liquid 82 was 0.8 Pa · s.

  Next, as shown in (c) of FIG. 3, the entire amount of foam 41 collected in the beaker 71 was added to the thickening liquid 82 and mixed. Thereby, the viscous bubble liquid concerning a present Example with which the foam 41 was disperse | distributed to the thickening liquid 82 as a bubble was obtained.

  The bubble diameter, volume, bubble diameter distribution, void ratio, and disappearance ratio in the viscous bubble liquid obtained from the foam 41 were measured.

  FIG. 4 is a cross-sectional view showing an apparatus used for measuring physical properties of bubbles in the obtained viscous bubble liquid.

  In order to measure the physical properties of bubbles in the viscous bubble liquid, first, a petri dish 92 containing the viscous bubble liquid is placed on the turntable 91 as the sample 93, and the sample 93 is irradiated with laser light. And the physical property of the bubble in a viscous bubble liquid is measured by imaging the projection image of the bubble in the sample 93 with the camera 95 attached to the optical microscope, and performing image analysis.

  In addition, since the light transmittance is lowered when the thickness of the sample 93 is increased, in this embodiment, in order to reduce the thickness of the sample 93, the laser 94 and the camera 95 were arranged in the vertical direction and the measurement was performed. .

  Below, the measuring method of said each physical property is demonstrated.

(Bubble diameter)
An image captured by the camera 95 is displayed by a paint application, and a circle is superimposed on the edge of each bubble as shown in FIG. 5B, for example. And the diameter of this overlapped circle was measured as the bubble diameter.

(Bubble volume)
By calculating the volume of the imaging part from the two-dimensional size (vertical and horizontal size) and the focal length of one image captured by the camera 95, the volume of all bubbles in the image was calculated. .

(Bubble diameter distribution)
In one image captured by the camera 95, the volume of the imaged portion is calculated from the two-dimensional size (vertical and horizontal size) of the image and the focal length, and the number of bubbles in one image is calculated for each bubble diameter. All were counted and converted per ml. Thereby, the number of bubbles for each bubble diameter per 1 ml of viscous bubble liquid was determined.

(Void void rate)
The ratio of the volume of the bubble to the unit volume of the viscous bubble liquid from the volume of the entire viscous bubble liquid in the imaging portion calculated by the above method and the sum of the volumes of all bubbles (volume content of bubbles) Was calculated as the void fraction of the bubbles.

(Bubble disappearance rate)
The produced sample was sealed and stored in a cool and dark place, and the void ratio was measured immediately after production, after 3 days from production, 7 days from production, and 35 days from production. The elapsed days and the void rate are shown in a graph, and an approximate line is drawn by the following calculation formula to determine the disappearance rate per day.

  That is, when the void ratio of the viscous bubble liquid is B and the disappearance ratio is λ, the relationship of the following equation (1) is established.

−dB / dt = λB (1)
Therefore, when equation (1) is solved, the following equation (2) is obtained. In the formula (2), _{B 0} represents an initial value immediately after production.

B = B ₀ × exp (−λt) (2)
Here, when the equation (2) is obtained by an approximate straight line from the plot of the actual measurement values, B ₀ = 0.3756 and λ = 0.049. At this time, t is a day unit.

(Measurement result)
(A) of FIG. 5 is a figure which shows the optical microscope photograph of the said viscous bubble liquid immediately after manufacture, (b) of FIG. 5 is 3 days after manufacture when it refrigerated at 5 degreeC after manufacture. In the optical micrograph of the said viscous bubble liquid, it is a figure which piles up and shows the circle for measuring a bubble diameter on the edge of a bubble.

  In addition, FIGS. 6 to 9 show the volume distribution of the viscous bubble liquid immediately after the production, 3 days after the production, 7 days after the production, and 35 days after the production, in order. Further, the transition of the void ratio at this time is shown in FIG. 10, and the transition of the elapsed days and the void ratio is shown in Table 1. In all cases, the viscous bubble liquid after production was stored at 5 ° C. in a refrigerator.

  FIG. 11 shows the bubble diameter distribution of the viscous bubble liquid after 3 days from the production.

  According to the present Example, as shown in FIGS. 6-9 and FIG. 11, the bubble of diameter 2mm or less, for example, maximum diameter 1.6mm, was able to be obtained stably.

  Further, according to this example, as can be seen from FIG. 10, when it is assumed that a void ratio of 10% or more is necessary, there is a life of about 25 to 30 days, and thus a viscous bubble liquid that is easy to handle is obtained. You can see that

  Here, for comparison, a normal bubble having a diameter of 1 mm obtained by a normal method (that is, a bubble having a diameter of 1 mm generated by blowing air into a liquid such as water) in the liquid. FIG. 12 and Table 2 show the rising speed and the moving time.

  The bubble rising speed and moving time were calculated from the following equation (3).

(Bubble rising speed)
Bubble rising speed is V∞, bubble radius r, gravity acceleration g, liquid viscosity μ, liquid density ρf, bubble gas density ρb, and balance of buoyancy, gravity and Stokes resistance. From the following formula, V∞ = (ρf−ρb) / 6πμr × (4 / 3πr ³ ) × g (3)
(See Non-Patent Document 2).

(Bubble travel time)
From the rising speed, the time required for bubbles to move 10 cm in the viscous liquid was calculated.

  As shown in FIG. 12 and Table 2, a normal bubble having a diameter of 1 mm is less than 1 minute if it is a liquid having a viscosity of about 0.8 Pa · s like the thickening liquid 82 used in this example. The liquid will escape. As shown in FIG. 12 and Table 2, even if the viscosity of the liquid is increased to 10 Pa · s, the time required for the 10 cm bubble to move is about 30 minutes. It turns out that it will come off.

  As described above, according to the results shown in Patent Document 1 and FIG. 12 and Table 2, bubbles disappear in a conventional contrast agent at a speed that is not an exaggeration to say instantaneously.

  On the other hand, as shown in FIG. 10 and Table 1, the viscous bubble liquid obtained in this example not only has a void rate of 10% or more immediately after production, but also has a bubble disappearance rate of 10 per day. % Or less (4.9% / day in the example shown in FIG. 10) and a very slow disappearance rate. In the example shown in FIG. 10, it is considered that a void ratio of 10% or more can be maintained for 25 to 30 days, and the void ratio of bubbles remaining after 35 days from the actual production is 7.1. It can be seen that the void ratio of 5% or more is maintained.

  For this reason, the said viscous bubble liquid is very suitable for an ultrasonic test | inspection, By using this viscous bubble liquid as a contrast agent, the contrast agent which was remarkably excellent in handleability compared with the former can be provided. In addition, by using the viscous bubble liquid as a contrast agent, it is possible to prepare a large amount of a contrast agent containing bubbles, which has been impossible in the past. Can be greatly improved. Further, by using the viscous bubble liquid as a contrast agent, it is possible to take a longer time for one ultrasonic inspection than before. Furthermore, it is possible to expand the inspection object, for example, it becomes possible to inspect the inspection object having a length that could not maintain the bubbles until the time of imaging with the conventional contrast agent.

  Note that the void ratio of the viscous bubble liquid (that is, the ratio of the volume occupied by the bubbles in the viscous bubble liquid) may be appropriately set according to the application so as to ensure the required void ratio at the time of use. Well, not particularly limited.

  FIG. 13 shows a contrast image (ultrasonic echo image) using the viscous bubble liquid obtained in this example as a contrast agent.

  FIG. 13 is a contrast image obtained when an ultrasonic inspection is performed from the outside by passing a tube through water and passing viscous bubble water through the tube.

  In FIG. 13, viscous bubble water in which bubbles of 1 mm or less are dispersed is used, and the bubbles are observed separately, so that it is understood that the ultrasonic resolving power is at least about 1 mm.

  As mentioned above, according to the said form and Example, the viscous bubble liquid which can hold | maintain a bubble over a long time, its manufacturing method, and the manufacturing apparatus of a viscous bubble liquid can be provided.

  As described above, the viscous bubble liquid according to the above embodiments and examples can be suitably used as a contrast agent in ultrasonic examination.

  For example, in the medical field, it can be used as a contrast agent for examining swallowing function, a contrast agent for examining abnormalities in the oral cavity, a contrast agent for examining abnormalities in the lumen of the digestive system, and the like. .

  Further, in the industrial field, it can be suitably used as a contrast agent in non-destructive inspection or the like of parts that cannot be seen from the outside such as in various pipes.

  In addition, since the viscous bubble liquid according to the above-described embodiments and examples can contain a large amount of bubbles, various types can be obtained by appropriately selecting and changing the type of gas contained in the bubble and the type of viscous liquid in which the bubbles are dispersed. It can be used as a functional viscous liquid. Examples of such a functional viscous liquid include functional viscous water containing bubbles, such as hydrogen viscous water and carbon dioxide viscous water.

  In addition, since the method and apparatus for producing a viscous bubble liquid according to the above-described embodiments and examples can change the texture of food by containing bubbles, the method and apparatus for changing the texture of foods Can also be used.

[Embodiment 3]
In the present embodiment, a method for storing (preserving) the viscous bubble liquid will be described below with reference to FIGS. 3 (a) to 3 (c), FIG. 14, and FIG. In the following, for convenience of explanation, components having the same functions as those in the first and second embodiments are denoted by the same reference numerals, and description thereof is omitted.

  Unlike the conventional case, the viscous bubble liquid produced by the method described in Embodiments 1 and 2 can stably store bubbles in the liquid for a long time. However, when the viscous bubble liquid is stored at normal pressure (atmospheric pressure), the void ratio decreases at a rate of 10% / day or less.

  Therefore, in this embodiment, the viscous bubble liquid is stored under pressure (ie, pressurized storage) in order to improve the decrease in the void ratio. For this purpose, in the present embodiment, the storage container for storing the viscous bubble liquid is internally pressurized.

  According to the present embodiment, by pressurizing the inside of the storage container and increasing the internal pressure in this way, the decrease in the void ratio of the viscous bubble liquid during storage is suppressed, and bubbles are stably contained for a long time. Can do. For this reason, according to this embodiment, the manufacturing frequency of the said viscous bubble liquid can be reduced, and the complexity of inspection work can be eliminated.

  The material and shape of the storage container are not particularly specified and may be any storage container that can withstand the pressurization inside the container (hereinafter referred to as “pressurized storage container”). A commercially available container can be used as the pressurized storage container.

  The internal pressure of the pressurized storage container is not particularly limited as long as it is higher than atmospheric pressure. In the present embodiment, for example, when the gauge pressure of the pressure device at normal pressure (atmospheric pressure) when the pressurized storage container is not pressurized is 0 MPa, the internal pressure of the pressurized storage container is, for example, 0 in terms of gauge pressure. The viscous bubble liquid was stored under pressure so that the pressure was 1 MPa or higher (that is, atmospheric pressure + 0.1 MPa or higher).

  In addition, as for the viscous bubble liquid, the decreasing rate of a void rate is so low that the internal pressure of a pressurized storage container is high. For this reason, the upper limit value of the internal pressure of the pressurized storage container is not particularly limited.

  However, in order to increase the internal pressure of the pressurized storage container, a container that can withstand the internal pressure is required. For this reason, in this embodiment, from the viewpoint of pressurization resistance and availability of the pressurized storage container, and reduction of capital investment, the internal pressure of the pressurized storage container is, for example, 0.5 MPa or less in terms of gauge pressure. did. When the internal pressure of the pressurized storage container is 0.5 MPa, the reduction rate of the void ratio can be suppressed to be extremely small as compared with the case where the viscous bubble liquid is stored at atmospheric pressure.

  Needless to say, however, when a pressurized storage container having high pressure resistance is used, the internal pressure of the pressurized storage container can be set higher.

(Pressurized storage method for viscous bubble liquid)
Below, the pressure storage method of the said viscous bubble liquid is demonstrated more concretely.

  First, a viscous bubble liquid to be stored was manufactured. The viscous bubble liquid was manufactured according to the manufacturing method shown in FIGS. 3A to 3C described in the above [Example].

  Specifically, first, water in the electromagnetic cooking pan 62 was heated to about 85 ° C. by the electromagnetic heater 61 in the step shown in FIG. Thereafter, while stirring the water (warm water) in the electromagnetic cooking pan 62 with the stirrer 64, the lecithin as the surfactant and the “gel-up WM” as the gelling agent are each set to a water content of 0.00. 3% by weight was added and stirred for 10 minutes. Thus, an aqueous solution 81 in which the above lecithin and “gel-up WM” were dissolved was prepared.

  Next, as shown in FIG. 3B, the aqueous solution 81 is transferred to a beaker 65, and bubbles are generated by a bubble generating device 69 connected to a pressurizing device while keeping the temperature constant at 65 ° C. A foam 41 was formed. As the bubble generating device 69, “Foamest” (registered trademark) was used. A compressor 68 was used as the pressure device, and the pressure was set to 0.2 MPa. All the foams 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 were collected in another beaker 71 shown in FIG.

  Next, water in another beaker 72 is kept at about 85 ° C. by the electromagnetic heater 61, and “Thoroughness up perfect” is added as a thickener at a ratio of 1% by weight to the water and stirred for 10 minutes. Thus, a thickening liquid 82 shown in FIG. 3C was produced.

  Next, as shown in (c) of FIG. 3, the foam 41 was mixed with the thickening liquid 82 and stirred to disperse the foam 41 in the thickening liquid 82, thereby producing a viscous bubble liquid.

  The mixing ratio of the thickening liquid 82 and the foam 41 was 500 cc of the foam 41 with respect to the thickening liquid 82 of 300 cc. After the viscous bubble liquid having the above mixing ratio was produced a plurality of times, each of the produced viscous bubble liquids was mixed and stirred to be homogenized, divided into 200 cc storage samples, and stored in a 300 cc pressurized storage container.

  As the storage samples, three pressurized storage samples were manufactured by pressurizing a pressurized storage container so that the internal pressure became 0.3 MPa by the atmosphere, and one non-pressurized normal pressure storage sample was manufactured.

  In addition, the pressurized storage container is pressurized with each one of the pressurized storage samples pressurized so that the internal pressure is 0.1 MPa, 0.3 MPa, and 0.5 MPa as gauge pressure. One non-atmospheric storage sample was produced.

  Each physical property of the pressure storage sample was measured immediately after the production, and after 7 days and 14 days from the production, by opening the pressure storage sample one by one. On the other hand, each physical property of the normal pressure storage sample was measured for the same sample immediately after production, and after 7 days and 14 days after production.

  In addition, as shown in Table 4, each physical property of the sample in which the internal pressure of the pressurized storage container was changed was measured immediately after the production, and after 7 days and 14 days from the production. In addition, the measurement items and measurement methods of each physical property of the sample are the same as in the above [Example], and in the same manner as in the above [Example], the bubble diameter, the volume of the bubble, the bubble diameter distribution, the void ratio of the bubble, The disappearance rate of bubbles per day was measured.

(Measurement result)
FIG. 14 is a graph showing the transition of the void ratio of the viscous bubble liquid when the internal pressure is applied to the pressurized storage container and when it is not applied.

  Table 3 shows the void ratio of the viscous bubble liquid immediately after production, and after 7 days and 14 days from the production when the internal pressure is applied to the pressurized storage container. It is shown together with the disappearance rate of bubbles per day in the storage period.

  As shown in Table 3 and FIG. 14, the void ratio immediately after the production of the viscous bubble liquid was 57.8%. Further, the void ratio after 7 days from the production was 55.5% for the pressure storage sample and 29.3% for the normal pressure storage sample. Further, the void ratio after 14 days from the production was 36% for the pressure storage sample and 23% for the normal pressure storage sample.

Further, the rate of disappearance of bubbles per day was measured in the same manner as in [Example]. That is, when the void ratio of the viscous bubble liquid is B and the disappearance ratio is λ, the relations of the expressions (1) and (2) are established. Therefore, with the void ratio B (ie, y = B) on the y-axis and the elapsed days t (ie, x = t) on the x-axis, the equation (2) is approximated from the measured value plot shown in FIG. As a result, in the case of a pressurized storage sample, B ₀ = 0.6171 and λ = 0.034. In the case of a normal pressure storage sample, B ₀ = 0.5374 and λ = 0.066.

  Therefore, as shown in Table 3, the disappearance rate of air bubbles per day for the normal pressure storage sample in the storage period of 14 days is 3.4% / day for the pressure storage sample, and 6.6 for the normal pressure storage sample. 6% / day.

  From the above results, it can be seen that the bubbles in the viscous bubble liquid can be stably stored when the viscous bubble liquid is stored under normal pressure as compared with the case where the viscous bubble liquid is stored at normal pressure.

  In addition, for the sample in which the internal pressure of the pressurized storage container was changed, the bubble diameter, the volume of the bubble, the bubble diameter distribution, the void ratio of the bubble were separately measured in the same manner as in the above [Example], and the disappearance of the bubble As a rate, the reduction rate of the void rate when the internal pressure of the pressurized storage container was changed was measured.

  FIG. 15 is a graph showing the decreasing rate of the void ratio of the viscous bubble liquid after 7 days from the production when the internal pressure of the pressurized storage container is changed.

  Table 4 shows the change in the void ratio of the viscous bubble liquid immediately after production and after 7 days from production when the internal pressure of the pressurized storage container is changed. It is shown together with the decreasing rate of the void ratio.

  When the internal pressure of the pressurized storage container is changed as shown in Table 4 and FIG. 15, the decreasing rate of the void ratio of the pressurized storage sample in the pressurized storage container after 7 days from the production is 0.1 MPa. 15.8% (= 57.8% -42%), 2.8% at 0.3 MPa (= 57.8% -55%), 1.3% at 0.5 MPa (= 57.8% -56) 0.5%). Moreover, the decreasing rate of the void rate of the atmospheric pressure storage sample after 7 days from manufacture was 28.5% (= 57.8% -29.3%).

  From the above results, the viscous bubble liquid has a decreasing rate of the void rate as the internal pressure of the pressurized storage container increases, and the internal pressure of the pressurized storage container is, for example, 0.5 MPa or less, more preferably 0.3 MPa or less. It can be seen that the decrease in void fraction can be reduced by storing under pressure than when storing at normal pressure.

[Embodiment 4]
The following will describe another embodiment of the present invention with reference to FIGS. 3A to 3C and FIG. In the following, for convenience of explanation, components having the same functions as those in Embodiments 1 to 3 are denoted by the same reference numerals, and description thereof is omitted.

  In the present embodiment, the relationship between the temperature of hot water containing a surfactant and a gelling agent and the void ratio of the viscous bubble liquid will be specifically described using experimental examples.

(Void ratio of viscous bubble liquid when water temperature of aqueous solution 81 is changed)
In the following, as a simple experiment, in the above [Example], a case where a viscous bubble liquid is produced by generating bubbles by changing the temperature of the aqueous solution 81 containing the surfactant and the gelling agent. An example will be described. However, it goes without saying that the same tendency can be obtained even when the liquid 42 is used instead of the aqueous solution 81 as the hot water.

  Below, the manufacturing method of the viscous bubble liquid concerning this embodiment is demonstrated. In addition, as above-mentioned, also in this embodiment, the viscous bubble liquid was manufactured according to the manufacturing method shown to (a)-(c) of FIG. 3 as described in the said [Example].

  Specifically, first, water in the electromagnetic cooking pan 62 was heated to about 85 ° C. by the electromagnetic heater 61 in the step shown in FIG. Thereafter, while stirring the water (warm water) in the electromagnetic cooking pan 62 with the stirrer 64, the lecithin as the surfactant and the “gel-up WM” as the gelling agent are each set to a water content of 0.00. 3% by weight was added and stirred for 10 minutes. Thus, an aqueous solution 81 in which the above lecithin and “gel-up WM” were dissolved was prepared.

  Next, as shown in FIG. 3 (b), the aqueous solution 81 is transferred to a beaker 65, and bubbles are generated by a bubble generating device 69 connected to a pressurizing device while keeping the temperature constant. Formed. In this embodiment, the same operation is performed except that the temperature of the aqueous solution 81 in the beaker 65 is maintained at 45 ° C., 50 ° C., 55 ° C., 60 ° C., 65 ° C., 70 ° C., and 75 ° C., respectively. Bubbles were generated at temperature. Then, the foams 41 accumulated on the liquid surface of the aqueous solution 81 in each obtained beaker 65 were collected in separate beakers 71, respectively.

  In this embodiment as well, “Foamest” (registered trademark) is used for the bubble generating device 69. Further, a compressor 68 was used as the pressurizing apparatus, and the pressure was set to 0.2 MPa.

  Next, water in another beaker 72 is kept at about 85 ° C. by the electromagnetic heater 61, and “Thoroughness up perfect” is added as a thickener at a ratio of 1% by weight to the water and stirred for 10 minutes. Thus, a thickening liquid 82 shown in FIG. 3C was produced.

  Thereafter, as shown in FIG. 3 (c), each thickening liquid 82 put in separate beakers 72 and foam 41 generated at each temperature recovered in each beaker 71 are mixed and stirred. Then, each foam 41 was dispersed in the thickening liquid 82 in each beaker 72 to produce each viscous bubble liquid. In addition, the mixing ratio of each thickening liquid 82 and each foam 41 made the foam 41 500 cc with respect to 300 cc thickening liquid 82.

  And the physical property of each viscous bubble liquid manufactured immediately after manufacture manufactured in this way was measured, respectively. The measurement items and measurement methods for the physical properties of the sample are the same as in the above [Example], and in the same manner as in the [Example], the bubble diameter, the volume of the bubble, the bubble diameter distribution, and the void ratio of the bubble are determined. It was measured.

(Measurement result)
FIG. 16 and Table 5 show the void ratio of each viscous bubble liquid obtained by changing the temperature of the aqueous solution 81 containing the surfactant and the gelling agent.

  As shown in Table 5 and FIG. 16, the temperature of the aqueous solution 81 containing the surfactant and the gelling agent was changed to 45 ° C., 50 ° C., 55 ° C., 60 ° C., 65 ° C., 70 ° C., and 75 ° C. In this case, a change was found in the void ratio of the obtained viscous bubble liquid.

  That is, as shown in Table 5 and FIG. 16, the void ratio peaks when the foam 41 is produced with the temperature of the aqueous solution 81 kept at 60 ° C., and at 50 ° C., 55 ° C., 65 ° C., and 70 ° C. before and after that. When the foam 41 is manufactured, the void ratio slightly decreases. In addition, when the temperature of the aqueous solution 81 was 45 ° C. and 75 ° C., the void ratio tended to be extremely reduced as compared with the case where the temperature of the aqueous solution 81 was 60 ° C.

  From the above results, when the foam 41 is manufactured, the temperature of the aqueous solution 81 containing the surfactant and the gelling agent is maintained within a range of 50 ° C. to 70 ° C., and the foam 41 is manufactured. It can be seen that the void ratio can be improved in each stage as compared with the case of producing a viscous bubble liquid using the foam 41 produced by maintaining the temperature at 45 ° C. or 75 ° C.

[Embodiment 5]
Still another embodiment of the present invention will be described below with reference to FIGS. 3A to 3C and FIG. In the following, for convenience of explanation, components having the same functions as those in the first to fourth embodiments are denoted by the same reference numerals, and description thereof is omitted.

  In the present embodiment, a case where the viscous bubble liquid is a functional food will be described.

(Functional food)
When the viscous bubble liquid is used as a food, as described above, a gas that is harmless to the human body is used as the gas introduced into the aqueous solution 81 containing the surfactant and the gelling agent. At this time, by using, for example, a gas having a function such as an antioxidant effect as the gas, the viscous bubble liquid can be used as a functional food. Examples of the functional food include a hydrogen gas-containing food containing hydrogen gas as bubbles.

  Hereinafter, in this embodiment, the case where hydrogen gas is used as the gas will be described as an example. Also in this embodiment, the viscous bubble liquid was manufactured according to the manufacturing method shown in FIGS. 3A to 3C described in the above [Example].

  Specifically, first, water in the electromagnetic cooking pan 62 was heated to about 85 ° C. by the electromagnetic heater 61 in the step shown in FIG. Thereafter, while stirring the water (warm water) in the electromagnetic cooking pan 62 with the stirrer 64, the lecithin as the surfactant and the “gel-up WM” as the gelling agent are each set to a water content of 0.00. 3% by weight was added and stirred for 10 minutes. Thus, an aqueous solution 81 in which the above lecithin and “gel-up WM” were dissolved was prepared.

  Next, as shown in FIG. 3B, the aqueous solution 81 is transferred to the beaker 65, and bubbles containing hydrogen gas are generated by the bubble generating device 69 connected to the pressurizing device while keeping the temperature constant at 65 ° C. By doing so, a foam 41 containing hydrogen gas was formed.

  In this embodiment, since hydrogen gas is used, the experiment was performed while the upper part of the beaker 65 was covered, an exhaust line was installed, and the hydrogen detector leaked was monitored.

  As the bubble generating device 69, “Foamest” (registered trademark) was used. Further, a compressor 68 was used as the pressurizing apparatus, and the pressure was set to 0.2 MPa. All the foams 41 accumulated on the liquid surface of the aqueous solution 81 in the beaker 65 were collected in another beaker 71 shown in FIG.

  Next, water in another beaker 72 is kept at about 85 ° C. by the electromagnetic heater 61, and “Thoroughness up perfect” is added as a thickener at a ratio of 1% by weight to the water and stirred for 10 minutes. Thus, a thickening liquid 82 shown in FIG. 3C was produced.

  Next, as shown in FIG. 3C, the foam 41 is mixed with the thickening liquid 82 and stirred to disperse the foam 41 in the thickening liquid 82, thereby containing hydrogen gas as bubbles. A viscous bubbling liquid was produced.

  The mixing ratio of the thickening liquid 82 and the foam 41 was 500 cc of the foam 41 with respect to the thickening liquid 82 of 300 cc.

  And the physical property of the viscous bubble liquid manufactured in this way immediately after manufacture and 7 days after manufacture was measured. In addition, the measurement items and measurement methods of each physical property of the sample are the same as in the above [Example], and in the same manner as in the above [Example], the bubble diameter, the volume of the bubble, the bubble diameter distribution, the void ratio of the bubble, The disappearance rate of bubbles per day was measured.

(Measurement result)
FIG. 17 and Table 6 show the transition of the void ratio of the viscous bubble liquid in the viscous bubble liquid containing hydrogen gas as bubbles.

  As shown in Table 6 and FIG. 17, the void ratio of the viscous bubble liquid was 42.5% immediately after production and 23.4% after 7 days of production.

As described above, when the void ratio of the viscous bubble liquid is B and the disappearance ratio is λ, the relationship of the above formulas (1) and (2) is established. y = B), and the x-axis is the elapsed days t (that is, x = t), and the equation (2) is obtained from the actual value plot shown in FIG. 17 using an approximate straight line, B ₀ = 0.425, λ = 0.085.

  Therefore, the disappearance rate per day of the viscous bubble liquid was 8.5% / day, and the viscous bubble liquid stably stored hydrogen gas bubbles at a high concentration.

  As described above, the foam 41 in which hydrogen gas is encapsulated as a gas in a film containing a surfactant and a gelling agent is an aqueous solution containing a thickener, and the viscous bubbles dispersed in the thickening liquid 82 The liquid was found to be able to maintain the hydrogen gas in a high concentration state for a long time by using hydrogen gas as the gas introduced into the aqueous solution 81 containing the surfactant and the gelling agent.

Therefore, the viscous bubble liquid can be used as a functional food. For example, by drinking the viscous bubble liquid, the viscous bubble liquid can be taken into the body in a state containing high-concentration hydrogen gas. Hydrogen molecules (H ₂ ) taken into the body in the state of high-concentration hydrogen gas induce liver hormone “FGF21” and promote energy metabolism, thereby improving obesity and diabetes. In addition, antioxidation is expected by incorporating hydrogen into the body as hydrogen molecules. Hydrogen is effective for anti-aging, arteriosclerosis, diabetes, spots, wrinkles, cataracts, etc. due to its antioxidant action.

[Summary]
In the viscous bubble liquid according to the aspect 1 of the present invention, the foam 41 in which a gas is included in a film containing a surfactant and a gelling agent is contained in a viscous liquid (liquid 43, thickened) made of an aqueous solution containing a thickener. The liquid 82) is dispersed as bubbles.

  As described above, bubbles are a good reflection source of ultrasonic waves, for example, and it is desired to develop a bubble liquid having a long bubble life. However, the time during which bubbles are present in the bubble liquid is usually extremely short as 1 minute or less, and it is no exaggeration to say that it is instantaneous. Even Patent Document 1 can extend the lifetime of bubbles only from about 5 minutes to about 10 minutes.

  However, the viscous bubble liquid of the above aspect 1 has a very slow bubble disappearance rate, and can significantly extend the life of the bubbles as compared with the conventional case.

  In particular, the viscous bubble liquid according to Aspect 2 of the present invention has a configuration in which the disappearance rate of the bubbles is 10% / day or less in Aspect 1.

  Further, the viscous bubble liquid according to aspect 3 of the present invention is the above-described aspect 1 or 2, wherein the void ratio of the bubbles in the viscous bubble liquid is 5% or more (for example, according to the experimental results shown in FIG. 5% or more and a maximum of 42.8%).

  The viscous bubble liquid concerning aspect 4 of this invention has the structure whose diameter of the said bubble is 2 mm or less in any one of the said aspects 1-3.

  Therefore, the viscous bubble liquid concerning the aspects 1-4 of this invention can be used conveniently as an ultrasonic contrast agent, for example. By using the above-mentioned viscous bubble liquid as a contrast agent, it is possible to provide a contrast agent that is remarkably superior in handleability than before.

  The viscous bubble liquid concerning aspect 5 of this invention has the structure in which the said viscous bubble liquid is a functional food in any one of the said aspects 1-4.

  Examples of the functional food include a hydrogen gas-containing food containing hydrogen gas as bubbles.

  That is, the viscous bubble liquid according to the sixth aspect of the present invention has a configuration in which the gas is hydrogen gas in any one of the first to fifth aspects.

  A viscous bubble liquid in which a foam 41 in which hydrogen gas is included as a gas in a film containing the surfactant and the gelling agent is dispersed in an aqueous solution (liquid 43, thickening liquid 82) containing a thickener is By making the gas into hydrogen gas, the hydrogen gas can be maintained in a high concentration state for a long time in the bubbles.

  Therefore, the viscous bubble liquid can be used as a functional food containing hydrogen gas reliably and stably. Hydrogen has an antioxidant effect and is effective for anti-aging, arteriosclerosis, diabetes, spots, wrinkles, cataracts and the like.

  In addition, the method for producing a viscous bubble liquid according to Aspect 7 of the present invention increases the foam 41 formed by introducing gas into warm water (liquid 42, aqueous solution 81) containing a surfactant and a gelling agent. In this method, bubbles are dispersed in a viscous liquid (liquid 43, thickening liquid 82) made of an aqueous solution containing a viscous agent.

  Moreover, the manufacturing method of the viscous bubble liquid concerning the aspect 8 of this invention is a method in which the mixture ratio of the said surfactant and a gelatinizer is 1: 1 in the said aspect 7.

  Moreover, the manufacturing method of the viscous bubble liquid concerning the aspect 9 of this invention is the said hot water in the state which the formation of the said foam maintained the temperature of the said warm water in the range of 50 to 70 degreeC in the said aspect 7 or 8. The method is carried out by introducing the gas into the above.

  Furthermore, the viscous bubble liquid production apparatus (viscosity bubble liquid production apparatus 1) according to aspect 10 of the present invention is a viscous bubble liquid production apparatus used in the method of producing a viscous bubble liquid according to aspect 7 or 8 above. A first container (for example, heating / stirring device 11 or heating device 51) containing warm water (liquid 43, thickening liquid 82) containing a surfactant and a gelling agent, and a viscous liquid made of an aqueous solution containing a thickener. A second container (for example, a heating device 31) to be put in, a gas introducing device (for example, the porous microbubble generator 13 or the swirling flow microbubble generator 53) for introducing gas into the warm water in the first container; The foam container 41 formed on the liquid surface of the warm water by connecting the first container and the second container and introducing gas into the warm water in the first container is used as the second container. Foam moving part to move to (foam moving part 20) , And a.

  In addition, the viscous bubble liquid manufacturing apparatus according to aspect 11 of the present invention is the above aspect 10, wherein the first container and the second container are provided so as to be able to be sealed, and the pressure in the first container. The pressure control mechanism (for example, the pressure control mechanism which consists of the compressor 12 or the water flow pump 52, the pressure gauge 15, and the relief valve 16) is provided.

  Moreover, the viscous bubble liquid manufacturing apparatus according to Aspect 12 of the present invention has the configuration according to Aspect 10 or 11, wherein the gas introducing device is a porous fine bubble generator (porous fine bubble generator 13). is there.

  Moreover, the viscous bubble liquid manufacturing apparatus according to aspect 13 of the present invention has the configuration in the aspect 10 or 11, wherein the gas introducing device is a swirling flow type fine bubble generator (swirl flow type fine bubble generator 53). is there.

  Moreover, the manufacturing apparatus of the viscous bubble liquid concerning the aspect 14 of this invention is the structure by which the said foam moving part is heat-retained with the heat insulating material (heat insulating material 22) in any of the said aspects 10-13.

  According to the method for producing a viscous bubble liquid according to the above aspects 7 to 9 and the viscous bubble liquid production apparatus according to any of the above aspects 10 to 14, the above-described viscous bubble liquid that can hold the bubbles for a long time is provided. Can be manufactured. In particular, as shown in the aspect 9, when the foam is formed by introducing the gas while maintaining the temperature of the warm water within a range of 50 ° C. to 70 ° C., the temperature of the warm water is 45 ° C. or 75 ° C. The void ratio can be improved by introducing the gas while maintaining the temperature as compared with the case where the foam is formed.

  Moreover, the storage method of the viscous bubble liquid concerning the aspect 15 of this invention is a method of storing the viscous bubble liquid concerning any one of the said aspects 1-6 under pressure.

  Further, the storage method of the viscous bubble liquid according to the sixteenth aspect of the present invention is the same as that of the fifteenth aspect, in which the storage container that stores the viscous bubble liquid is When the gauge pressure is 0 MPa, the viscous bubble liquid is stored by pressurizing the pressure device so that the gauge pressure is 0.5 MPa or less.

  Further, the storage method of the viscous bubble liquid according to the aspect 17 of the present invention is the storage container for storing the viscous bubble liquid in the aspect 16, wherein the internal pressure is 0.3 MPa or less in terms of the gauge pressure of the pressure device. This is a method of storing the above-mentioned viscous bubble liquid under pressure.

  According to the method for storing the viscous bubble liquid according to any one of the above aspects 15 to 17, the bubbles in the viscous bubble liquid can be held for a long time. Therefore, according to the said aspect, the storage method of the storage method of the viscous bubble liquid which can contain and store a bubble stably for a long time can be provided.

  The viscous bubble liquid of the present invention has a significantly longer bubble life than conventional ones, and can be suitably used as a contrast agent in ultrasonic examination or functional viscous water. The viscous bubble liquid production method and production apparatus of the present invention can be suitably used as the above-described contrast agent and functional viscous water production method and production apparatus, and for example, a method for changing the texture of food. It can also be used as a device.

DESCRIPTION OF SYMBOLS 1 Viscous bubble liquid production apparatus 10 Foam formation part 11 Heating / stirring apparatus (1st container)
11a Container 11b Lid 12 Compressor (pressure control mechanism)
13 Porous microbubble generator (gas inlet)
14 Stirrer 15 Pressure gauge (pressure control mechanism)
16 Relief valve (pressure control mechanism)
20 Foam moving part 21 Connecting pipe 21a Opening part 21b Opening part 22 Insulating material 30 Foam mixing part 31 Heating device (second container)
31a Container 31b Lid 32 Stirrer 41 Foam 42 Liquid 43 Liquid 51 Heating device (first container)
51a Container 51b Lid 52 Water Flow Pump (Pressure Control Mechanism)
53 Swirl flow type fine bubble generator (gas introduction device)
53a Intake port 53b Intake port 53c Discharge port 61 Electromagnetic heater 62 Electromagnetic cooking pan 63 Thermometer 64 Stirrer 65 Beaker 66 Stirrer 67 Stirrer 68 Compressor 69 Bubble generator 71 Beaker 72 Beaker 81 Sample 94 Laser 95 Camera

Claims (4)

Viscosity used in a method for producing a viscous bubble liquid in which foam formed by introducing a gas into warm water containing a surfactant and a gelling agent is dispersed as bubbles in a viscous liquid composed of an aqueous solution containing a thickener. An apparatus for producing bubble liquid,
A first container for containing warm water containing a surfactant and a gelling agent;
A second container for containing a viscous liquid composed of an aqueous solution containing a thickener;
A gas introducer for introducing gas into the hot water in the first container;
The first container and the second container are connected, and bubbles formed on the liquid surface of the warm water are moved to the second container by introducing gas into the warm water in the first container. An apparatus for producing a viscous bubble liquid, comprising: The first container and the second container are provided so as to be able to be sealed,
The apparatus for producing a viscous bubble liquid according to claim 1 , further comprising a pressure control mechanism that controls a pressure in the first container. A method for producing a viscous bubble liquid in which a foam formed by introducing a gas into warm water containing a surfactant and a gelling agent is dispersed as bubbles in a viscous liquid composed of an aqueous solution containing a thickener ,
Using the viscous bubble liquid production apparatus according to claim 1 or 2, the foam is formed by introducing the gas into the warm water in the first container, and the formed foam is A method for producing a viscous bubble liquid, wherein the liquid is dispersed as bubbles in the viscous liquid by being moved to the second container. The viscous foam liquid according to claim 3 , wherein the foam is formed by introducing the gas into the hot water while maintaining the temperature of the hot water within a range of 50C to 70C. Manufacturing method.